The Geminal Model and The Fourier Transform Method For The Evaluation of Multicenter Slater Integrals

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P A R T R I D G E , H A R R Y • III
THE GEMINAL M O D E L AND T H E FOURIER T R A N S F O R M
M E T H O D FOR T H E E V A L U A T I O N OF M U L T I C E N T E R
SLATER INTEGRALS*
I N D I A N A U N I V E R S I T Y , P H . D . , 1979
University'
, Microfilms
International joon .j i t o m o a i >. a v n * m d o «, m p a r i o g
THE GEMINAL MODEL AND THE FOURIER TRANSFORM METHOD
FOR THE EVALUATION OF MULTICENTER SLATER INTEGRALS
Harry Partridge III
December 1978
Partially supported by grants from the
National Science Foundation
Principal Investigator: Harrison Shull
Submitted to the Faculty of the Graduate School in partial
fulfillment of the requirements for the degree of Doctor of
Philosophy in the Department of Chemistry, Indiana University.

December 19* 1978
This is to certify that the thesis submitted by Harry Partridge III

has been accepted by the Ph.D. Advisory Committee as satisfactory in
partial fulfillment of the requirements for the Ph.D. degree.
Chairman ^
(Research Adviser)
Acknowledgements
The author would like to express his gratitude to Professor
Harrison Shull and Professor Stanley Hagstrom for their guidance
and support throughout the course of this work.
The author Is Indebted to Dr. James Sims for his assistance
during the early stages of the work and to all of the members of
the Quantum Chemistry Group at Indiana University, Dr. James
Sims, Dr. John Rumble, Dr. Robert Howard, Edward Piute, Fernando
Ornellas, and Irene Waight, for many helpful and stimulating dis
cussions.
The author is also grateful to his parents, Helen and Harry
Partridge, to Penny Posthumus-Meyjes, and to Irene Waight for
their invaluable assistance in the preparation of this manuscript.

THE FOURIER TRANSFORM METHOD FOR THE
EVALUATION OF MULTICENTER SLATER INTEGRALS

1
The energy expectation value of a system is given by
E = <¥|ft|V>/<Y|Y>
A
where H is the hamiltonian of the system and y is the approximate eigen
function, If V is approximated with a linear combination of antisymme
trized products of one electron functions, then the energy expression
for atomic and molecular systems reduces to a linear combination of one
and two electron integrals over the one electron orbital basis func
tions, The evaluation of these integrals is an essential step in any
calculation.
The orbital bases used in ab Initio calculations today are
principally of two types: Slater or exponential and gausslan type
orbitals.
v r r - v"'1
$ r lan ■ v n"
where N is the appropriate normalization constant and the Y£m are the
normalized spherical harmonics. Both of these basis sets are complete
in the limit of an infinite expansion^" and the choice of a one electron
basis is in many ways a matter of convenience. Slater orbitals offer a

2
number of advantages over gaussian orbitals, however:
a. The exact one electron wave function of a one electron system
in a central attractive coulomb field can be written as a finite linear
combination of Slater type orbitals or an infinite expansion of gaussians.
b. A Slater basis satisfies the cusp condition at r ** 0 and has the
correct exponential decay for large r. A finite gaussian basis will not
satisfy the cusp condition and decays too fast for large r.
It is thus not surprising that fewer Slater type orbitals than
gaussian type orbitals are required to achieve a given accuracy of approx-

3
imation. Slater orbitals appear to provide an efficient basis with which
to describe electron distributions in many electron systems.
In spite of the obvious advantages of Slater type orbitals, most ab
initio calculations on polyatomic molecules have used a gaussian type
basis. This is due essentially to the ease in computing multiccnter in
tegrals over a gaussian basis and the difficulty in obtaining accurate

5
Integrals over Slater orbitals. In some cases, the evaluation times for
Individual multiccnter Integrals over gaussians may be on the order of
1000 times less than the computation time for the corresponding integral
over Slater type orbitals.
For many calculations, a gaussian basis set is clearly the more
efficient, even considering that a larger one electron basis is needed.
If one is attempting to obtain highly accurate results then the advantage
of using gaussians becomes less clear. As the basis set increases, the
integral computation time becomes less of a stumbling block. The

g
integral transformation becomes the time consuming, critical step.
In addition, since the number of integrals increases as N**, where N is

the size of the basis set, the data handling problems in performing
large scale MC-SCF and Cl calculations become excessive. A Slater
orbital basis, giving a more compact expansion, is thus often desir
able, and more efficient.
The difficulty in using a Slater basis, however, is the general
unavailability of computer routines to compute accurate multicentcr
integrals over Slater orbitals, particularly over higher angular

*
momen-
turn orbitals. Several recent studies have shown the importance of in
cluding these polarization orbitals,^ and indicate that the principal

O
error in large scale Cl calculations is in the one electron basis.0
In this work we are concerned with the Fourier transform
method, its implementation and use for the computation of multicenter
two electron repulsion integrals over s,p and d type Slater orbitals.
Multicenter Electron Repulsion Integrals
We are primarily Interested in the evaluation of the multi
center two electron integral
I - kiz "1!
- / / d 3rxd3r2Aab(ri) |rx-r2|_1Acd(r2)
where (r) is the charge distribution arising from the product of
orbitals located on centers a and b. Wien a gaussian orbital basis is
used, the integrals may be efficiently evaluated.^ This 1b due to the
fact that the product of two gaussians on centers a and b may be

expressed as a single gaussian on a third center. This permits asimple
reduction of all three and four center electron repulsion Integrals to
two center integrals. When a Slater orbital basis is used no similar
reduction is possible and special methods must be used.
Numerous studies on the evaluation of multicenter Slater inte
grals have been reported in the literature. The general approaches for
their evaluation may be classified as:
1. The expansion of the orbitals about a single center.
2. The bipolar expansion and the expansion in elliptical
coordinates.
3. The potential function method .12
4. Numerical Integration techniques.13
5. Integral transform methods.14
6. The transform convolution theorem and expansion methods.15
In addition, special methods are available for the limiting
cases of one and two center integrals. Several recent reviews have
compared the relative merits of the various methods.-’ The analytic
expression derived by Silverstone using the convolution theorem
appears to be computationally Intractable. The expansion methods
suffer from rather poor convergence and difficulty in evaluation of
the expansion coefficients. Product formula numerical Integration
techniques require a large number of quadrature points or functional
evaluations to compute the five or six dimensional integrals; no
completely satisfactory technique Has 1)660 found to treat the integrand
singularity,'*'® Non-product numerical integration formulas have not yet
reached the level of sophistication needed to obtain the required
accuracy. ^
The potential function method is a powerful and accurate method.
It has the advantage that its implementation is roughly independent of
the 1-quantum numbers involved. In practice, the method appears to be
too slow to be useful — at least for non-linear integrals over s, p,
and d orbitals.
The transform methods have recently received considerable atten
tion and at present appear to be the most efficient method of calculating
molecular repulsion integrals. Stevens and Shavitt hove developed

18
routines based on the alternate gaussian transform method which is
formally equivalent to the Fourier transform method. Their routines com
pute the multicenter s, p, and d Integrals involving d orbitals only on
one center. Lin has extended this work to include all integrals involv-
19
ing d orbitals. The above routines, however, are not charge distribu
tion oriented; they compute all of the integrals in a given canonical
orbital block simultaneously. For example, they compute the 625 (dd/dd)
integrals arising from the different m-quantum numbers together. In
addition, many of the integrals involving d orbitals are not explicitly
coded; the parametric differentiation formulas are generated as needed.
The authors report that, in general, their routines are expensive to use.
Hagstrom has developed an efficient charge distribution oriented

20
algorithm based on the Fourier transform method. His routines, how
ever, are limited to s and p type orbitals. In this work we consider
modifications and extensions of Hagstrom's routines to improve

efficiency and to Include integrals over d type orbitals. The formula
tion, computational effort and convergence of the method are considered.
Fourier Transform Method
The Fourier transform method for the evaluation of multicenter
Slater electron repulsion integrals was introduced by Bonham, Feacher
and Cox. They showed that by using the relationship
i?, - ;2f - <2^)-'/ask clC •
we may effect a separation of the variables r^ and r^. This is done at
the expense of introducing a three dimensional integration over k but
it significantly reduces the mathematical and computational complexity
of the integrals.
We are interested in evaluating the integral
1 ' < *° *3 I ru " ‘ I ♦?>
where the orbitals are normalized real Slater type orbitals

♦
N _ r(2a)2n'fl~|^
Nn* |_ (2n) j J
where are the normalized real spherical harmonics.
Using the transform (2) or equivalently, the Fourier convolution
theorem, we may express the integral (1) as

7
I - (27T2)"1/ d3k k“V b(k)A^d(-k)e"lk‘rac (A)
where A ,+is the fourier transform of the charge distribution

ab
Aab(k) “ / d 3r4-°(r)«b (r-rab)e"ik-r (5)
To evaluate this transform for an arbitrary Slater type orbital,
we use the appropriate parametric differentiation operator An£m defined
such that
An*»*ls - *nltm
where ^giB a Is Slater type orbital on the same center as ♦n&n and
having the same orbital exponent. The A operator for s, p, and d
orbitals are given in Table I.
Therefore, we have
(7)
The general electron repulsion Integral over arbitrary Slater type
orbitals can be obtained by differentiation of integrals over Is
orbitals.
(8 )
TABLE I
PARAMETRIC DIFFERENTIAL OPERATORS FOR SLATER TYPE ORBITALS
A3 A(**>
î
(_ A ' tti-1
nsa Sc
npa (- 6 »"'1 V
6C
nd i"'3 p 0
v + »a YaDa><-£ 2 _ 26 2
( - 1 V
65
a a
Where
? The orbital exponent

Q.
D ■ /S » ^ ^ 6 \ (x , y , z )
a ’ 'a’ a
-a %x (, t:1
a •'a a
a , a i a
Wj. ^ 2»
i a a i a
*SU>2* ”“1» *3^
3uJ
The general Slater orbitals np and nd are defined as:
np ■ oi np + u. np + w np„
r x rx y y z rz
nd - w0nd2 ^ (n1ndx2_y2 + u2ndxy + u3ndxz + nd.

yz
The general p and d orbitals are characterized by the appropriate
<i) vector. We refer to this as the M quantum number of the orbital.

9
SLATER ORBITALS (NOT NORMALIZED)
ns * rn_I e“txr
npx = rn“2x e " C tr
"Py = rn-2y
npz » rn“2z e~Qtr
nd2z - (3z2-r2)rn"3 e-ar
ndx 2-y2 " (x2-y2)rn~3 < -ar
ndxy - Xy rn“ 3 e"ar
ndxjj - xz rn“3 e"ar
ndyz “ yz rn“3
Fourier Transform of Two Center Slater Orbital Products
The Fourier transform of a two center charge distribution has
been studied by several researchers. Its evaluation has been attempted

22
by: (a) Expanding the shifted function about the origin, (b) Expand-
23 21
ing in elliptic coordinates and (c) Using the Feynman identity.
Its computation, however, has proven to be difficult, especially for
highly asymmetric charge distributions; as a result, none of the compu
tational schemes that have been developed is completely satisfactory.
The formulation of Bonham, Preacher and Cox obtained using the Feynman
identity, is the most practical and is utilized in this work. Below
we outline its derivation.
We wish to evaluate the transform
I - / d * r e~ * 0-C*|r-R|
Using the transform relation
e-l-l -
we may express X as:
i jt / “ik*R m _ i(k.(s+R)
I- ( 2 H ) - * ( j f o / d ’k ^ ^ / d ’s ^ ’ e
where the substitution s » r - R has been made. Performing the integral
over s we obtain
2 52 C s ik.R
I - 4it 6?6c' j d3k (k2+e2) (C2+|k+k| 2)
/ a
11
Using the Feynman Identity

.1
(ab)-1 •»f 0 du[a + u(b-a)]2
followed by the change of variable p « q + uk we obtain
2 ,/' au / - - 1 P -R
1 " ¥ W t 'h du e J d p 7pi5 F 7 2
_ i-n 62 / j,. -iuk.R -R^f
■ 2* acif'A du e % -
" 2’>Rs5 C ' t - i i ) 2 /^duu(l-u)aluk-R f *
where
Z = R/M
M - U ’)2 + (C2-C,2)u + u(l-u) k2 (10)
Introducing the auxiliary functions,
U0 (z) - « ' R “l e"z

(ID
Un(z) - CC'RZn“l kn(z)
Zn
where kn (z) are the modified spherical Bessel functions of the 3rd kind;
we now have
i + 4
/ du
0
U(l-U) u 3(z) e iuk,R (12)
12
For the general case, further simplification of this Integral Is not
possible and numerical Integration techniques are used.
The computational difficulties arising in the evaluation of
this integral are easily seen. For large orbital separation, i.e., for
large R, the integrand will be highly oscillatory. For asymmetric charge
distributions the integrand will vary rapidly near one of the endpoints.
This is due to the large variations in Z arising from the term
(C2-(C,)2)u -(C1)2. If C»C* then Z and the integrand will vary rapidly
near the u ■ 0 endpoint. In addition, os k increases the integrand be
comes highly peaked about each endpoint. If (c |2+C2) « k 2, C'2 «* C2
and k.R - 0 then the maximum of the integrand is at approximately
max
1 - X
where
Xmax " ^ U3(CR)[5U3(t;R) + Ua(CR)]"1
Plots of the integrand with q.R - 0 are given in Table II exemplifying
the above difficulties.
The problems involved in evaluating the two center Fourier
transform using equation (12) may also be understood by noting that the
integrand becomes singular near the range of integration. For k ■ 0,
the singularities occur at
c
and u =
TABLE II
Symmetric Is Charge Distributions
o
n
CM
rzm
to
1*
Legend
LJ
Z=1
Z=2
Z=3
14
^ =3
p
Lm
-J 10 rxOO
rwrwN
910 910 hlO 210 010 900 hOO

czin
15
Asymmetric Is Charge Distributions
r»
to
oj
fzm
to
LEGEND
0=1 0=1
P=1 0=1?
P=1 0=3
P=1 fl=S
0=1 0=7
16
Therefore, as the charge distributions becomes more asymmetric, the
singularity moves closer to the range of integration. For k j* 0, the
singularities occur at
» \ (1 ± A + A C ’) if C - V
Vr
Thus, as k increases, the singularities move closer to the range of
integration. The implications of the "nearby" singularities on the
accuracy of the computation ore easily seen by considering the error
term for a Gauss Legendre quadrature scheme. The error for an n point
formula on a finite interval [n,b] is given by2^
b-a .2n+l 2n** n 1**

F2n(h) a < h < b
n K 2 > (2n+l) [(2n) t]*4
where f2n(h) is the 2n th derivative of the integrand. As the singular
ity moves closer to the range of Integration the bound on the derivative
Increases. We thus require a larger quadrature scheme to obtain the
same degree of accuracy. It should be noted that since the integrand
is continuous on the interval [0,1], we are assured that a Gauss
Legendre quadrature scheme will converge as n, the number of quadrature

2 *5
points, approaches infinity. J
The above difficulties led Harris to abandon numerical integra
tion methods.26 They replaced the integral, equation (12), by a sum of
integrals over subintervals, and introduced the Lommel expansion for the
modified Bessel functions in each subinterval.

17
They evaluated these Integrals analytically and found the con
vergence to be quite good when small enough Intervals were used.
Their procedure, however, involves a large number of points
and, while adequate for expanding a single two-center charge distribu
tion, is largely unacceptable for the calculation of electron repulsion
integrals. This unacceptability is due to the fact that product quadra
ture schemes are necessary. Furthermore, the difficult "parts" of the
integral are the subintervals near the endpoints. This suggests that
a composite Gauss Legendre quadrature with a small subinterval near
such endpoint be used. This procedure has been found to be very
practical in most instances and is used in this work. The selection of
the nodes and the number of quadrature points for each subinterval will
be discussed with the computational methods.

Formula for ($is$i8lri2 _1
With the use of equation (12) for the Fourier transform of the
a b
Îs^ls ‘’âr8e distributions, we may express the multicenter repulsion
integral over Slater orbitals as:
1 - <*1A» >
.1
t t
/ d3k k 2 J rill u(l-u)U3
Mil \ tl m (z„u)
(• e*k ra rab
ab
t
^ d v v(l-v)Uj(zc{j)e lk*(rc vrcd^
where U(za^) and U(zc^) are the auxiliary functions for the correspond
ing charge distributions. In order to emphasize the dependence on the
integration variables, we write
U (z .) - U (u,k)
n oo n
V zcd> - V v ’k)
Performing the angular integrations in equation (13) we obtain
I ■ 8tt / dk
/ 0 /0
f
du u(l-u)U3 (u,k)
/0
f
dv v(l-v)V3 (v,k)jo(kp)
where jo(kp) is the spherical bessel function and

19
General Formula for I

1 j k 1
a b
Using equation (12) for the Fourier transform of a
charge distribution and the parametric differential operators, equation
(6), we have for an arbitrary charge distribution
A^b(k) » 2tt A*a J ^*duu(l-u)Us (u,k)e±k'^ra~urab^ (17)
o 2tt / ' d u u d - u j U C ^ j r C ^ J j e ^ ^ V ^ a b 5
Jo iJ i j
*4*
The column array U (#..$,,) ■ U (u,k) depends upon the orbitals describ-
1 j ij
ing the charge distributions; the column operator matrix r(4>j$j) oper-
ates on the nuclear position vector rQ and r^. The general multicenter
integral may thus be written os
I - (r ia- *
8u / dk/ duu(l-u)^ dwd-vJUj. (u,k)F1,k|[(u,v1k)Vw (v,k) (18)
where
FijU “ rij+ û*R5 rkS.(v,k^ fo^kp^ (l9)
The differential operators in Tônd may be expressed in terms of

a
the operator R where
R " (kp) 6(kp>
The matrix v,k) is seen to depend on all four orbital indices. In
particular it depends on the 1 and M quantum numbers of each orbital,
but is Independent of the principal quantum numbers, n, and the orbital
exponents.
20
Table III lists the and P ^ for the various charge distri
butions involving up to d-Slater type orbitals. The table assumes
n = £. + 1. The extension to higher principal quantum numbers is
straightforward and will be discussed with the computational proce
dures. In general, further analytic simplification of equation (18)
does not seem possible and as a result the remaining integrations are
done numerically.
TABLE III
Row Uy
‘ij
1 U3 1
1Salsb
lsa2Pb 1 (l-u)r6b 3 1
2 uCl-u)^
1 -urfu3
2 Pa1Sb
2 uCl-u)^.
1 u(l-u){-r^3 +
2 Pa2 Pb
2 u2 (l-u)TgU^ —ra
7
3 u d - u ) 2^
4 u 2(1-u )2U5
l 7l 7
3d Is, 1 u2 riU 3 + u (6 u 0 “ uF2 Û«t " u2 r3U5

a b
2 -2u2(l-u)Ult r-
3 u 2 (l-u)2Us rf
to
22
cd j - cd in
id Cm t-
C i d ^ Cdtnat'atMat'' id j - id in
C- C- t- C -. Cm Cm t-. C-H
in
nPn
r-i
rO ID
C-t
CM
3
I a
ra
c-.
3
I
3
I. cdm t"~ ID
a r*
ao jSn a m a
3 cm 3 t-> a m
^ (fin
<3(-> w I Cm 3
Cm
a /m
III - Contd
a cm I 3
i 3 I
a C** cfo ' l.
1 m 3
ido
3 3
3 /-N I in in
I 3
I
a +in a
a °
S3°
cd m
a a cm /M
id I Cm a cm
J3 CO cdiM ^ r"s
f—« *3 IdCM Cm a m 3
TABLE
CM a m J m I 3
i Id rH a o Cm Id CM I.
I
in
Ci
a © 1 I
id o a „ ■ :
3 I a cm a o
ac- in Id CM Cm Id m
a a O Id CM Cm J a o
a *3 3 Cm a CM 3
cd O Cm a
I 3 +
3 a <->
id o m w a mi a
a a Cm I a
%M» J a - * mm id m H a rM m
3 Cm + Cm Cm a
id #m J- 3 rM a rM
+ Cm
r-s & 1 J.
3
I.
ro a 3 r-» a 3
a a in in in (d rM Id CM n I
•3 in in Pm _a a A Cm Cm a m
a CM a u> CM ID V a CM CM Cm CM
10^ rM CM r “M Cm \ a 9 Cm ^ d o
Cm r"N 3 m v_r 3 m w* 3 m
a+Ml 9| X3
/~N 3 I r*N r—x 1 /M I. r—x
3 1 pH 3 3 pH 3 3
I. H w 1 1 1 9 Cm 1-1 I I
•m T CM H rH m r—t 1 id CM CM
CM 3 i~ r 3 w rH Cm 3 3
3 CM CM CL CM m w CM CM
*3 CM 1 3 3 1 3 9 + + I
CM m v j- m a c- rH CM cn
rf? •a
CM cn
•» <
•H a
m m
TABLE III - Contd.
Row
ij
4 2u2 (l-u)2 [uTfult + (6uJ - uTj)U5 - u T|u 6 ]
5 u2(i-u)2 [urfus + (6wo ~ ■* urfuy ] Ts
6 4u2 (l-u)2U (i-u)rja - ur;
7 4u 3(1-u )3U6 rf
a b
8 -4u3(l-u)3Us r„r*
b a
9 2u*a-u)UV6 r r
ab
10 -2u*a-u)\ r r
A 5
11 u’Hl-u)1*!^ rarb
5 5
is>
W
2It
Where
r?
1
» r+
aby1a rab
.
rf = Trace
r? “oc* t, - Orbital Exponent
rf = rabY?;
fip
n
rf 6 % 6
P aJ
rf - w+ r ,
_a _ab
ra
”7 w+ 6
r fb - U+Y 5
„a ,b j
m
rio rab
iJ/
i
r1Jk-
r»i v A
UJ ■ (j
l u
ab a b
Yab
u “ Ha. b
25
This table assumes the charge distribution is on centers AB. The
corresponding formulas for charge distributions on centers CD are easily
obtained by the transformations:
a ■+ c, b d
u+ v
U-
n*- Vn
6 -*.-6
P P
Thus, for example:
2 pc2 pd v(l-v){-r6 r6 V3 + 1
v2 (i-v)r6 V1<
v(i-v)r^
v2 (l-v)2V
9
Algorithm for the Multicenter Integral Evaluation
The multicenter electron repulsion integral, equation (18), is
to be evaluated using a gausslan product quadrature formula. The
finite u and v integrations are to be computed using a Gauss Legendre
quadrature formula. The semi-infinite k integration is to be computed
with a Gauss-Laguerre quadrature scheme or by inverting the integration
range to (0,1) and then using a Gauss Legendre scheme. We have
I - <*“+J 1 ^ 1 *c
u4 > <u •k) F1Jki(u •10vki (v'k) (21)
where the u's are the weights of the corresponding quadrature points.
The number of integrand evaluations needed to evaluate a multicenter
electron repulsion integral thus appears to have an dependence.
Since the difficulty in evaluating the integrand increases rapidly with
the sum of the 1 quantum numbers, we must require that the desired
accuracy be obtainable with a relatively small N. In addition, we
need to reduce the N dependence of the computation by using "parts"
of the computations for many integrals. In order to accomplish this,
we must recognize that
a. The U^(u,k) are charge distribution quantities and may be
used for all integrals involving that particular charge distribution.
Furthermore, if the u and v quadrature schmes are identical then the
Ujj(u.k) and V ^ ^ k ) are the same.
b. The F-raatrix, F (u,v,k) depends only on the 1 and M quantum

J KA
numbers for fixed nuclear centers. All integrals with the same 1,M
quantum numbers should be done simultaneously.

27
c. The integration, equation (21), or the corresponding
summation may be written as
I » E tuk E Wu U ., (u,k) G..j-(u,k) (22 )

k u J J
where the G-vector, Gjjk|(u,k) *s given by
Gijkl(u .k) - E wvFijkl(ufv,k) Vkl(v,k) (23)
The G-vector may then be used to compute a set of integrals
corresponding to the set of {U^}. For a sufficiently large number

2
of integrals, we have an N dependence on the number of integrand
evaluations.
In the following, we summarize an algorithm utilizing these
considerations. Table IV summarizes the various steps.

TABLE IV 28
Algorithm for the Fourier Transform Method
Initialization (Part I Processing)
1) Input
2) Form a list of the needed charge distributions. The charge
distributions are to be linked together by centers and by l,tn
quantum numbers which are called IPQ blocks.
3) Calculate the charge distribution constants and allocate stor
age for the 2-center U^(u,k). The 1-center (k) are also
computed at this time.
4) Allocate the remainder of the available storage for the needed
arrays. If insufficient core is available, partition the u
summation.
5) Load the appropriate set of routines for the integral type;
either coulomb or hybrid and exchange integrals.
Computation (Part II Processing)
Loop over k quadrature points

Specify k convergence tests (if any)
Loop over partitions of the u summation
Compute the needed set of small f's, the f^Ckp's)
Loop over the IPQ blocks for the specified centers
Compute the B-vectors, the U^(u,k) if needed
Loop over u quadrature points

Compute the F-raatrix, îjklû*v,^ÎJ ^°r V"^* ôr
J“1* Nkl* for 1-1' Nij
Compute the G-matrix, ôr I-l. StJ
Compute the k contribution to the integral 1^
Test k convergence.
29
F-Matrix Computation
The F-matrix is defined by equation (19) as
Fijkl(u,V,k) “ rij<u *k>rkl<v,k)fo<kp) (19)
where the F's are the corresponding charge distribution operator
matrices defined in equation (17). Each is seen to operate on the co
ordinates of the nuclear position vector of the charge distribution
and thus may be expressed in terms of the coordinates of the vector p.
•+ -*• ■+ -v
p ■ r - ur + vr
ac ac cd
Table III gives the matrices for charge distributions involving
up to d type orbitals. Using these expressions, we may write the
F-raatrix for any case as
Fijkl(u*v *k) " Fijkl(u*v)?fo(kp)
where R, the column vectoroperator, isgiven by
& - (1, R, R|.... Rn)

A
in which the operator R is defined by equation (20).
R ■ -k2 __ § _
(kp) fi(kp)
and the dimensions of R are + 1
Defining
Rnfo(kp) - fn(kp) (25)

30
we have
Fijkl(u»v »k) “ Fijkl(u,v)-(kp) (26>
where
f « Rf (kp)
- 0
The matrix is independent of k and is a function only of
the 1 and M quantum numbers. It is a semi-Bparce matrix of dimension
Nf " Nijkl x nR wh®re Nijki “ Nij % i with and being the

dimensions of the corresponding T matrix. Letting each V be given by
t i l
we have the j column of given by
t f i j k l f c . v H j ‘ <2 7 >
where j ■ K x + I
For charge distributions involving s, p, and d type orbitals,
the r *s are one or a product of the following operators.

I
rf “ ?ab-A'P
's - 5pÂ§p
r7 ■ “a S p
rf ■ M»5 p
31
where ut and y specify Che M quantum numbers of Che p and d type

6 6 6
orbitals respectively and 6 is the operator (t- *T )* ^x “
P X Py P
rz
pressions are given in Appendix A for some of the cases which arise.
The computation of the F-matrix is the time consuming step of
a calculation and care must be taken in its implementation. The general
functional form of the F-matrix is specified by the 1 quantum number
and it is invariant to the Interchange of orbitals comprising the
charge distribution. For maximum efficiency, it is necessary that each
distinct coupling case be coded explicitly. The sparceness of the
F, „ matrix must be taken into account as well, i.e., none of the zero
ijkl
elements of the r matrices included.
In addition to this, since the F-matrix depends only on the 1
and M quantum numbers, we can minimize the number of F-raatrix cases
that ariBe by using canonical orbitals. Furthermore, calculations
involving d orbitals are simplified — by using canonical orbitals —
since the number of matrices arising are thereby limited. Each of the
matrices that occurB has no more than 2 nonzero elements, thus signifi
cantly reducing the matrix algebra involved. The matrices that arise
in the calculations and Borne needed tables are given in Appendix B.
The algorithm implemented is correspondingly restricted to
canonical orbitals and is summarized below. For each distinct coupling
case:
32
Loop over the u quadrature
Loop over nonzero (Tjj)j
Loop over nonzero (Fk^)j
Compute (Fjjk^(u,v,k)) j. j for all v quadrature points
Compute the G-vector
A comment regarding the use of the G-vector organization is
necessary. When the computation is arranged in this manner, we re
quire that k be an outer summation and thus we are not able to take
advantage of the fact that the F(u,v) matrix remains constant. Because
of the size of F(u,v) and the number of quadrature points used, it is
not practical to save this information; thus, the F(u,v) matrix must
be recomputed for each k. However, it must be noted that the number
of multiplications necessary to compute F(u,v) becomes rather large as
the 1 quantum number increases. It is thus necessary at least to con
sider making k the inner summation.
I « Z wu Z u>v Z wk Fi1 kl(u,v)f(kp)U (u,k)Vkl(v,k) (29)

u v k J J
Nevertheless, examining the expressions for the appropriate
number of multiplications per integral, Table V, we see that as the
number of charge distributions increases, the G-vector algorithm is
superior. An a and p orbital integral routine was written using each
algorithm. For (ss/ss) integrals the algorithm based on k-inner was a
factor of 2 slower than the G-vector algorithm for very small blocks and
became much slower as the number of orbitals increased. For a single
(pp/pp) integral the k-inner algorithm was slightly faster than the
G-vector.
33
With two sets of p orbitals, the G-vector scheme was clearly the more
efficient. For calculations involving d orbitals it is not certain
that enough d orbitals will be used to make the (dd/dd) integrals effi
cient using the G-vector scheme. However, most of the integrals that
arise do involve several s and p orbitals and these integrals need to
be efficiently computed. It is possible that another method should
be used to compute the (dd/dd) integral. If not with the k-inner
method, then by using another computational method.

34
TABLE V
NUMBER OF MULTIPLICATIONS NEEDED FOR INTEGRAL EVALUATIONS*
G-Vector Method - Equation (22)

V i * » . + “c W
NG-Vector ' W c C1 + NINr 1 IP«A) + ( ^ C H I P W
K-Inner Method - Equation (29)
IPQA)]
NK-mner " NI I<"» + W t V ' (IPQA)<IPqB) + V c (1 + Nr 1
For Very Large Blocks; IPQA, IPQC °°
N_ „ -► N, N_N
G-Vector k I c
N + N. N*N
K-Inner k I c
Where
N^ Number of u,v quadrature points
N^ Number of k quadrature points
N Dimension of U .
c ab
N Dimension of V .
r cd
N^ Average number of small f's used per row
N Number of multiplications necessary to calculate |J(u,v)
for each quadrature point
IPQA, IPQC Size of IPQ Blocks
* • •
Assuming U^'s and fn 's are given.
35
NUMBER OF MULTIPLICATIONS TO FORM F-MATRIX PER (u,v,k) QUADRATURE POINT
Case Ns N^ Nfc
(ss/ss) 0 1 0
(sp/sp) 1 1 5
(sa/pp) 1 1 5
(sp/pp) 8 1.5 20
(PP/PP) 25 1.69 52
(sd/as) 4 1 7
(sd/pp) 30 1.5 48
(sd/sd) 25 1.67 40
(aa/pd) 8 1.33 17
(ap/pd) 27 1.64 50
(PP/PP) 89 1.93 143
(pd/pd) 248 2.16 354
(pd/dd) = 608 2.44 796
(dd/dd) s 1300 2.73 1630

36
ESTIMATE OF NUMBER OF MULTIPLICATIONS PER INTEGRAL
PDPD CASE
Nj *»32 N^ ■ 36 (36,864 quadrature points)
IPQA- IPQC Vvector NK-Innor

Block Size--------- -------- --------
1 5,716,086 4,124,672
2 1,886,653
4 703,503 838,400
8 294,820 612,608
« 8,064 258,048
Computation of the Charge Distribution Quantities
The charge distribution quantities ^ (u,k) are expressed in
terms of the auxiliary functions U^ as defined in equation (11). We
have
. Uo " R“V Z
Un " R2 (- 5 > n - i “ R2n'- V 8>

Zn
where ^ and ^ are the respective orbital exponents and R the inter-
nuclear separation
Z - R/tl
M » Cj2 + Cj 2 )u + u(l-u)k2
The Un (z) are easily computed using the recurrence relation
V l (z> - t<2n-3)U„(Z) + U„_,CZ)]
The procedure is started using Uo and Ui, where Uo is given by
equation (1 1 ) and Ui is
Ui(z) *> R 2U 0 (z )/ z
The Ujj (u,k) are then evaluated by taking the appropriate linear com
binations of the Un 's. The tables given for the U ^ (u,k) assume
n ■ £+1, If ri > Jt+1 we must correct the formulas. This is easily
done by simply modifying the U^'s. The principal quantum number n of
an orbital is increased by the raising operator . The effect of

SC
this operator on the UR is given by
38
The operator ("£) does not affect the T operator matrix. If the
6C ij
raising operator does not operate on any part of the matrix, except
the UR, we may use the same equations given by Table III and simply
modify the Un 's. This is the case for all charge distributions except
those involving nd orbitals. The parametric differentiation

z2 -r2
operator for the nd^ 2 r 2 orbital involves the orbital exponent and
special care must thus be taken in the evaluation of the U^(u,k).
For the one center case, when R ■ 0, the u integration may be
done analytically. The U^'s can be simplified:
lim U - a a. (2n-l) I! M"(2n'1)/2 n>2

R-H) " a
The one center B-vectors may be expressed as a linear combination of
I(j,k,l).
/ J k
u (1 -u) Ugdu (3 1 )
Charge distributions involving only s and p orbitals can be expressed
in terms of
D* + 2)
where raises the principal quantum number, n. This quantity is
evaluated by noting that
IU.J.2) - D^-'WA,.) - [ f f i ) 1'1 - s g - z p (32)

39
where
° = ?a + i:b
“• * i l
n -6 1
°2 Tfo o
a1
ij (a2 + k 2)^
The evaluation Is accomplished by forming the table
W - Dim ” 2 I(n-l,n-l,n+l) - Dim-2 D2 n"2 (4Ai2) n,m >. 2
using the recursion relation
n
Di nn
D2 m ■ aDi n-1n i\ Din-1 _
D 2*1'” 1-(n-1)
t
D2 m+2
For charge distributions Involving d orbitals we need additional
Integrals of the form
I(j+.e, k+Z, j+k+e+1) - L^"1 L^"1 D2£(AAi2)
and
I<j.ktj+k)
where
La "
( A )I
Lb
( 4 ) i
40
The latter may be easily evaluated by using the Identity
u(l-u) - (1 -u) - (1 -u) 2
and we have
I(j,k,j+k) “ KJ-1, k, j+k) - I(j-1 , k+1 , j+k)
The integral given by equation (33) is evaluated by expanding the
product powers of Dj. This gives a polynomial operator equa
tion of degree j + k .
*<>+ V i + v >2 + •••• Aj+k » r k
The coefficients A. depend upon the orbital exponents t and . The

1 a b
Integral is obtained by taking the appropriate linear combination of
the W 's.
nm
Quadrature Schemes
The specification of the quadrature schemes is very important
as it determines the accuracy and the computation time of the repulsion
integrals. The quadrature specification is nontrivial since we are
computing the integrals in blocks. The quadrature scheme must be suffi
cient in each "region" to compute the "worst" integral in that given
region to the accuracy desired. In general, there is no omnibus quadra
ture scheme and the automatic selection of a scheme for a specified
accuracy is difficult without significantly overcomputing most of the
Integrals.
41
In the following sections, we discuss the optimum quadrature
schemes to use for the (u,v) and k Integrations for various types of
Integrals. We will then discuss the selection of quadrature schemes
for blocks of integrals and the procedures for computing large inte
gral blocks.
U, V Integrations
The quadrature scheme specification for the u and v integra
tions is of crucial importance since the computation time is very
sensitive to the number of u, v quadrature points. The computational
difficulties in evaluating the fourlcr transform of two center charge
distributions have already been discussed. The difficulties are
principally due to the singularities near the range of integration
resulting from large k values and from asymmetric charge distribu
tions. The above problems are reflected in the difficulty in repre
senting the charge distribution functions, U^j(u,k). A large
separation between the centers of charge distributions also causes
difficulty due to the oscillatory behavior of the modified spherical
Bessel functions, f^(kp) and thus the F-matrix.
Symmetric Charge Distributions
Integrals over symmetric charge distributions are generally
very easy to compute. The principal computational difficulty is the
highly peaked nature of the integrand for large k. This difficulty
can be handled by using a composite Gauss Legendre scheme including

42
a "small" subinterval near each endpoint. The following partition
has been found to be especially useful.
Jr' du t "
“ I du + I/•’“ du f'
+ I du
•'O •'0 •'•O'* •'•96
The quadrature schemeB used are represented by
(0,, n . .04, n . .96, n . 1.)

1 2 3
This Is usually given by just [n^, n^, n^] unless nodes of the subinterval
arc changed.
Table V compares the values of Integrals computed using several
u-v quadrature formulas.
Below we summarize the results for symmetric charge distributions.
1. For small k values the majority of the u,v quadratures arc
needed In the center region. The outer subintervols, however, cannot
be Ignored; a [2 , n, 2] quadrature is not sufficient.
2. For large k values we need considerably more points for
the outer sublntcrvals. The center region cannot be Ignored until k is
very large.
3. The difficulty in evaluating the integrals depends only
weakly on the size of the orbital exponents except as noted below.
4. A small separation between the charge distributions increases
the difficulty. This is due to the oscillatory nature of the modified
spherical Bessel functions.

43
5. The difficulty often increases as the distance between
centers of a charge distribution increases. The larger difficulty
arises from the greater variations in the p vector as a function of
u. P is given by
■+
p = r + vr - ur ,
ac cd ab
and for large r or r the p vector will vary considerably with u.

ac ab
The F (u.v) matrix and the modified Bessel functions will be more
ijkl
difficult to represent. The effect of this is somewhat nullified by
the rapid decrease of the integral value with increasing r .
6 . An important consideration is the nearness of the centers
comprising the two charge distributions, particularly when the orbital
exponents of the two charge distributions are different. The effect is,
in many ways, similar to the difficulties arising from asymmetric
charge distributions. Consider the following hybrid Integral block:*
<clcl /c2c3>
C1 c2 c3
For these Integrals the p vector is given by
P “ r + vr
12 23
Since r is similar in magnitude to r ^ we will havelarge variations
in the p vector withv, in this case near v ■ 1.This effect is most
pronounced when compactorbitals are on center and diffuse orbitals
are on centers and C^. For example, the Integral (ls^,ls^/ls^,ls^)
is fairly difficult to compute while (Is ,1 8 ^/1 8 ^,1 8 ^), (la^,ls^/ls^,ls^)
and (l8 ^,ls^/lBy,ls^) are fairly easy to calculate.
SEE TABLE VI for an explanation of the center and orbital representation.

44
7. Higher principal quantum numbers only weakly a£fect the
accuracy and computational difficulty. Their effect is to introduce
nodes in the charge distribution quantities.
8 . Higher angular momentum orbitals generally present no
problem. Difficulty arises only for integrals that are zero in the
one center limit; the effect, however, is generally small.
9. It is Important to note that most of the computational
problems occurring in exchange integrals also are present in hybrid
Integrals. In testing the sufficiency of the u or v quadrature we
need only consider the appropriate hybrid Integrals for the charge dis
tributions involved.
Asymmetric Charge Distributions
The evaluation of multicenter electron repulsion integrals
becomes considerably more difficult with greater asymmetry of the
charge distributions. The asymmetry of the charge distributions skews
the charge distribution quantities, the U^(u,k), so they are peaked
closer to one of the endpoints, i.e., the endpoint corresponding to
the larger of the orbital exponents. As the charge distribution be
comes more asymmetric this skewedness becomes the dominant effect and
we need consider only this region. We may roughly symmetrize the charge
distributions, for k » 0 , with the transformation u' « ua where a is
the ratio of the orbital exponents. We must insure that the specified
u quadrature adequately describes the transformed coordinate, u'.

45
Asymmetric integrals can usually be accurately computed using
approximately the same number of quadrature points, but quadrature
schemes of the form (n^, n2 » n^) are inappropriate.
All of the computational problems occurring in the symmetric
case are also Important for the asymmetric case. They are compounded
by the difficulties caused by the asymmetry of the charge distributions.
Table VI compares the accuracy of various quadrature schemes
for a number of Integrals.
K-Integration
The k-lntegrand involves the highly oscillatory modified Bessel
functions, the fn(kp). This may lead to difficulty in convergence if
the integrand does not go rapidly to zero with increasing k. Fortu
nately, for most of the multi-center electron repulsion integrals
occurring in molecular calculations, the integrand dies off sufficiently
rapidly and excellent convergence is obtained.
The principal factors determining the difficulties in evaluating
the k-integral are the compactness of the charge distributions and the
distance separating the charge distributions. As the distance between
charge distributions increases, the magnitude of p increases, thus de
creasing the period of the Bessel functions while the value of the
Integrand decreases only slowly. For coulomb integrals where P“rac» we

find that the integrand decreases as 1/r . The compactness of the
charge distributions is an important factor since compact charge dis
tributions in real space are diffuse in k-space and vice versa. For
46
diffuse k-space functions, the integrand falls off slowly with k and
we must include large k values in the quadrature scheme. This again
causes problems because of the oscillatory nature of the integrand.
The difficulties involved in evaluating an integral are largely
specified by the Integral type; i.e., coulomb, hybrid or an exchange
type integral. Coulomb Integrals are generally the hardest to compute
since they involve compact, one-center charge distributions. Hybrid
Integrals are generally easier to compute since the 2 -center charge
distribution is usually rather diffuse — in real space. Exchange type
integrals are, in general, the easiest to compute since both charge
distributions are diffuse.
In addition, however, we may classify integrals as coulomb
like and hybrid-like integrals. A coulomb-like integral is either an
exchange or a hybrid integral where the two-center charge distributions
are compact. (This occurs, for example, with highly asymmetric charge
distributions or when the separation of the charge distributions is
large compared to the range of the charge distribution). The evalua
tion of the coulomb-like or hybrid-like integrals involve the same com
putational difficulties as the corresponding coulomb or hybrid integrals.
The following quadrature schemes have been found to be useful in
evaluating the k-integrals.
a. An n-point Gauss Laguerre quadrature. The convergence using
quadrature schemes of this form is fair. Large Gauss Laguerre quadrature
schemes are too heavily weighted for large k and many of the quadrature
points do not contribute effectively to the integral. This difficulty

47
may be easily rectified by using k-convergence tests to truncate the
expansion when the contribution to the integral Is sufficiently small.
Another procedure which has been found to be very effective is the use
of truncated n-point formulas. For example, utilizing the first 35 of
a 64 point quadrature scheme is effective. These quadrature schemes
are designated by (n) or (n /nj).
b. Using a mixed Gauss Legendre and Gauss Laguerre formula.
I - J°dkl(k) +
/ a
dkl(k) (36)
These quadrature schemes are effective; they permit accurate
computation of the Important region [0 ,a) and, especially when used in
conjunction with the k-convergence tests, allow for effective computa
tion of the tall. These quadrature schemes arc designated (nâ.nj)
with the scheme (nlt5,20) being particularly well liked. Quadrature
schemes of this form arc probably the best general purpose schemes.
c. A composite Gauss-Legcndre formula.
r - .\
1 ~ J 0dkI<k> - /„<* f<Tik> a V o n

A composite Gauss-Legendre quadrature formula allows for the very accur
ate computation of molecular Integrals. In general, however, quadrature
schemes of this form are somewhat complicated; three or four subintervals
may be necessary. The quadrature schemes, however, are useful for
coulomb-like integrals and for testing the convergence and importance
of different regions of k-space.
Table VII compares the quadrature schmes for various integrals.

48
INTEGRAL TABLES
The centers are represented by where i gives the distance in
atomic units, from the origin.
The orbital exponents are given by the index of the orbital. For
example, ls^ represents a Is orbital with an orbital exponent of 3.

49
TABLE VI
U-QUADRATURE CONVERGENCE TEST
U-Quadrature Schemes
A [1 2 , 24, 12 ]
B t 4, 8 , 4]
C t8, 8 , 8 ]
D [1 2 , 8 , 1 2 ]
E t 4, 12 , 4]
F [ 8, 12 , 8 ]
G [2, 12 , 8 ]
H [ 8, 12 , 2 ]
I [ 8 , 16. 8 ]
K-Qundrature Scheme of the Composite Gauss Legendre Form, Equation (37)
" (0*i .80, Dji .91* .97)

Integral Block (c c / c^) K Quadrature (32,0,0)
Difference from comparison value in 8 th decimal place where difference is

D(K) = 1(A) - I(K) K = B,C ,D,E,F,G,H,I
Comparison
Value
Integral A B C D E F G H I
(lS jlS j/lS jlS j) .41707527 -5 -5 -5 0 -13 0 1 0
(ls1 ls1 /ls1 ls3) .21938345 -2200 -2200 -2200 -6 -6 -6 -3189 0
.07330404 -1969 1697 1697 -3772 -165 -164 -210414 -7
(ls1 ls1 /ls3 ls1) .27035384 -3989 -3988 -3988 -17 -16 -6313 -16 0
(ls^ls^/ls^ls^) .10529200 -2628 3263 3264 -6132 -240 -328198 -240 -11
(ls3 ls3 /ls7 lSl) .14448494 -3449 5214 5215 -8994 -330 -471547 -330 -16
(ls7 ls7 /l8 lls7) .07775124 -2091 1769 1769 -4036 -175 -175 -222265 -8
(ls7 ls7 /ls7 ls^) .15056242 -3506 5616 5616 -9468 -346 -497037 -346 -17
(c C / c4 c5) K Quadrature (32,0,0)
(lS jls ^ /ls ^ S j) .19022905 0 0 0 0 0 0 0 0
(ls1 ls1 /ls1 ls3) .09189920 -906 -906 -906 -2 -2 -2 -1321 0
(ls_ Is.,/is. ls?) .03678575 -798 719 719 -1588 -70 -70 -89123 -3
Difference from comparison value in 8th decimal place where difference is
D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(c c / c^ c^) - Contd. K Quadrature (32,0,0)
(lSjlSj/ ls3 ls1) .08424748 -935 -935 -935 -2 -2 -1358 -2 0
(ls1 ls1 /ls7 ls1) .02995391 -759 766 766 -1595 -70 -89308 -70 -3
(ls3 ls3 /ls7 ls1) .02988085 -754 750 750 -1575 -70 -88727 -70 -3
(ls7 ls?/ls1 ls7) .030A8253 -783 705 705 -1559 -70 -70 -88132 -3
(ls7 ls7 /ls7 ls1) .03801134 -990 1043 1043 -2122 -88 -115285 -88 -4
( c c / CjC^ K Quadrature (0,32,0)
(lSjlSj/lS^lSj) -.00001204 1 1 1 0 0 8 0 0
(ls1 ls1 /ls1 ls3) .00007613 -3 -3 -3 0 0 0 -6 0
(lS^lSj/lSjlSy) .00007206 -1 1 1 -3 0 0 -185 0
(lS-jlSj/lSjlSj^ -.00019338 13 13 13 0 0 187 0 0
(ls1 ls1 /ls7 ls1) -.00031651 26 -41 -41 68 0 1805 0 0
(ls3 ls3 /ls7 lsl) -.00442111 171 -610 -609 782 0 25825 0 0
D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(c c / - 1"ontd. K Quadrature (0f32}0)
(lSylSy/lSjlSy) .00101298 82 -68 -68 148 -2 -2 111 0
(ls7 ls7 /ls7 ls1) -.00777347 -624 -1040 -1036 418 1 44213 1 -3
(c c / c^Cg) K Quadrature (0,32,0)
(lSjlSj/lSjlSj) -.00000048 0 0 0 0 0 0 4 0
(ls1 ls1 /ls1 ls3) .00001620 0 0 0 0 0 0 0 0
(lsjlsj/lsjls^ .00001699 0 0 0 -1 0 0 -60 0
(Is^ls^/ls^ls^) -.00002152 1 1 1 0 0 14 0 0
(lSjlSj/lS^Sj) -.00003141 2 -3 -3 0 0 0 0 0
(IS.jlS.j/lSylS^ -.00037580 18 -41 -41 60 0 1940 0 0
(ls7 ls7 /ls1 ls7) .00031368 21 10 10 11 0 0 -913 0
(ls7 ls7 /ls7 ls1) -.00064335 -8 -70 -69 61 0 3285 0 0
Ul
N
D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
**
(c c / c ^ ) K Quadrature (0,0,32)
(ls1 ls1 /ls1 ls1) -.00000001 0 0 0 0 0 0 0 0
(ls1 ls1 /ls1 ls3) .00000005 0 0 0 0 0 0 0 0
(lSjlSj/lSjlSy) .00000025 0 0 0 0 0 0 -1 0
(lS^Sj/lS-jlSj) -.00000022 0 *0 0 0 0 2 0 0
-.00000108 2 0 0 3 0 0 0 0
(ls3 ls3 /ls7 ls1) -.00005284 140 -15 -16 156 0 515 0 0
(lSylSy/lSj^lSy) .00006967 -61 12 12 -73 0 0 -515 0
(ls7 ls7 /ls7 ls1) -.00034359 890 -103 -108 995 1 3787 1 5
(c c / c^c5) K Quadrature (0,0,32)
(ls1 ls1 /ls1 ls1) .00000000 0 0 0 0 0 0 0 0
(ls1 ls1 /ls1 ls3) .00000001 0 0 0 0 0 0 0 0
(Is-ls./ls.ls-) .00000006 0 0 0 0 0 0 0 0
(
V
D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(c c / c^c5> - IContd. K Quadrature (0,0,32)
(ls1ls1/ls3ls1) -.00000002 0 0 0 0 0 0 0 0
(ls1ls1/ls7ls1) -.00000008 0 0 0 0 0 0 0 0
(1 8 2 1 8 2 /1 3 ^ 5 ^^) - .00000406 8 -1 -1 9 35 0 0 0
(lSylSy/lS^lSy) .00001993 -60 0 5 -66 -5 -5 -95 -5
(lS ^lS y/lS ylS ^ -.00002620 54 -7 -6 60 0 236 0 0

Integral Block (c / c^c^) K Quadrature (32,0,0)
Difference from comparison value In 8 th decimal place where difference Is

D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
Integral A B C D E F G. H I
(lSjlSj/lSjlS^ .31118396 1 1 1 0 0 0 0 0
(lSjlSj/lSjls^ .15744819 -1540 -1540 -1540 -4 -4 -4 -2247 0
(ls1 ls1 /ls1 ls7) .05228734 -1361 1204 1204 -2684 -118 -116 -150116 -5
(ls1 ls1 /ls3 ls1) .19263154 -2604 -2604 -2604 -9 -8 -3864 -7 0
(iSjlSj/lSylS^ .07295800 -1811 2113 2113 -4095 -169 -224193 -170 -8
(ls3 ls3 /ls7 ls1) .03423996 -799 993 993 -1875 -81 -105827 -82 -3
(ls7 ls7 /lsils7> .00142239 -38 33 33 -74 -3 -3 -4092 0
(ls7 ls7 /ls7 ls]L) .00216162 -48 59 59 -113 -5 -6613 -5 0
(lslls7 /lsils7) .01151088 -596 565 565 -1215 -53 -53 -68647 -2
(ls7 ls1 /ls1 ls7) .00803771 -410 344 344 -792 -36 -22767 -22761 -1
(lslls7 /ls7 lsi) .02099982 -977 1478 1478 -2559 -97 -68226 -68226 -4
(ls3 ls7 /ls7 lsi) .01473758 -402 410 410 -848 -35 -46932 -148 -1
Integral Block (c c^/ < ^ 3^ K Quadrature (0,32,0)
Difference from comparison value In 8 th decimal place where difference is

D(K) * 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(ls^lsj/lsjlsj) -.00000017 0 0 0 0 0 1 1 0
(ls^s^/ls^ls^ .00000070 0 0 0 0 0 0 3 0
(lS^j/l^lSy) -.00000740 0 -2 -2 2 0 -2 58 0
(ls1 ls1 /ls3 ls1) -.00000171 3 3 3 0 0 18 9 0
(ls1 ls1 /ls7 ls1) -.00002123 4 0 0 4 0 162 14 0
(ls3 ls3 /ls7 ls1) .00015673 -27 8 8 -36 0 -576 0 0
It
(ls^s^ls^lsy) -.00002186 1 -2 -2 3 0 0 104 0
(ls7 ls7 /ls7 lsi) .00003663 -4 3 3 -7 0 -168 0 0
(ls1 ls7 /ls1 ls7) .00006261 11 3 3 7 0 0 -346 0
(ls7 ls1 /ls1 ls7) .00003979 -9 20 20 -29 0 -371 -371 0
(ls1 ls7 /ls7 ls1) -.00066336 -2 -191 -190 189 0 3972 3972 0
(ls3 ls7 /ls7 ls1) -.00024282 -5 -30 -30 24 0 1616 9 0
Ui
ON
Integral Block (c c^/ C£C3) K Quadrature (0,0,32)

D(K) = 1(A) —I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(lSjlSj/lSjlSj) .00000006 0 0 0 0 0 0 0 0
(ls^lSj/lSjlSj) .00000001 0 0 0 0 0 0 0 0
(lS^lS^/ls^lSy) -.00000015 0 0 0 0 0 0 3 0
(ls^ls^/ls^ls^) .00000092 -4 0 0 -4 0 -6 -7 0
(lSjlSj/lSylSj) .00000474 -30 1 2 -32. 0 -27 -37 0
(lS^lS^/lSylSj^) .00004246 -186 1 7 -194 -5 -258 -54 -6
(IS 7lS yiS^Sy) .00000006 0 0 0 0 0 0 -1 0
(ISylSj/lSylSj) .00001187 -57 1 3 -60 -2 -65 -2 -2
(ISjlS^lSjlgy) -.00001371 64 -7 -7 72 0 0 267 0
(lSylS1/lS^lSy) .00000342 -10 1 1 -11 0 -28 -28 0
(lS^y/lSylS^) .00035670 -3028 81 196 -3225 -108 -2001 -2001 -115
(ls3ls7/ls7ls1) .00023646 -1051 5 45 -1094 -38 -1305 -504 -39

58
TABLE VI Contd.
U-QUADRATURE CONVERGENCE TEST
A [1 2 , 24, 12 ]
B [ 4, 8 , 4]
C [8, 8 , 8 ]
D t 4, 12 , 4]
E I8, 12 , 8 ]
F 1 4, 16, 41
G t2, 12, 8 ]
H [8 , 12 , 2 ]
I [ 8 , 16, 8 ]
Integral Block (ISjlSj/ls^lSj) K Quadrature (0,32,.8)

D(K) = 1(A) ~ I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(c c /c c ^ .50687938 -38 -38 -38 0 0 -73 -3 0
(c c /CjC2) .41707527 -5 -5 -5 0 0 -13 1 0
(c c /CjCg) .31597928 1 1 1 0 0 1 0 0
(c c /c3 c^) .24071174 0 0 0 0 0 0 0 0
(c c / c ^ ) .39532798 -31 -31 -31 0 0 -33 -33 0
(C .31118396 1 1 1 0 0 0 0 0
Cc C^CjC^) .23602178 0 0 0 0 0 0 0 0
(C C ^ C jCj ) .27646150 -20 -20 0 0 0 -31 -11 0
(c C ^ C j ) .23669355 -20 -20 0 0 0 -30 -10 0
.18468673 0 0 0 0 0 -1 0 0
(C C1/C2C4)
(C C j /C j C j ) .14210479 0 0 0 0 0 0 0 0
\D
Integral Block (ls^ls^/ls^ls^) K-Quadrature (.80,32,.91)
--------------------------- Difference from comparison value in 8 th decimal place where difference is
D(K) * 1(A) - I(K) K - B,C,D,E,F,G,H,I
Comparison
Value
(c c /c c^) .00016511 -7 -6 -6 -1 0 -93 7 0
(c c /cxc2) -.00001204 1 1 1 0 0 8 0 0
(c c /c2 c3) -.00000344 0 0 0 0 0 0 0 0
(c c /c3 c^) .00000311 0 0 0 0 0 0 0 0
(c ^ / c ^ ) .00002772 -3 -3 -3 0 0 -20 -20 0
(c c1 /c2 c3) -.00000017 0 0 0 0 0 1 1 0
(C Cj/CgC^ -.00000066 0 0 0 0 0 0 0 0
Integral Block (lSjlS^/lSjls^ K-Quadrature (.91,32,.97)
(c c /c c1) .00000036 0 0 0 0 0 -2 0 0
(c c /c2c3) .0 0 0 0 0 0 0 0 0
(c c /c.c ) .00000006 0 0 0 0 0 0 0 0
Integral Block (Is^ls^/ls^ls^) K-Quadrature (0,32,.80)

D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(c Cj/c^) .01344743 -3 -3 -3 0 0 1 -9 0
(C C j /C j C j ) .00904056 0 0 0 0 0 1 0 0
(C C^CjC,.) .00633476 0 0 0 0 0 0 0 0
(c Cj/c c2) .00003057 0 0 0 0 0 0 0 0
(c Cj/c^) .00002288 0 0 0 0 0 0 0 0
62
TABLE VI Contd.
BENZENE - INTEGRAL BLOCK (Cj Cj /c ^ )
Orbital Basis K Quadrature (20,5,36)
la 7.52232
Is. 5.12306
A
2s 1.83068
2s. 1.11528
A
A [ 24, 24, 24 ]
B [ 1 2 , 24, 1 2 ]
C t1 2 , 2 0 , 12 ]
D [ 1 2 , 16, 1 2 ]
E [12, 12 , 1 2 ]
F t 8 , 16, 8 ]
G [ 8 , 8 , 8 ]
H [ 4, 8 , 4]
Integral Block (c^^/c^c^)

D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(2 s,2 s/ls Is.) .00011076 0 0 0 0 0 0 0

A A
(Is Is /Is 2s ) .00009329 0 0 0 0 0 -7 -8
(Is lsA/ls 2s ) .00063108 0 0 -1 -5 -1 -24 -44
(Is 2s /Is 2s ) .01172934 0 0 -3 -151 -11 -849 -1915
(Is 2 sa/1 s 2 s ) .00948086 -3 -3 -6 -4 -63 +4260 -3616
(Is. 2 s/ls 2 s ) .01643723 0 0 -3 -142 -6 -2027 -25565

A
(Is. 2 s,/Is 2 s ) .01330632 -1 -1 -6 -172 -23 -535 -2193
A A
(Is 2s /Is 2 sA ) .01498122 -7 -7 -9 62 -120 6176 -8593
(Is 2 s,/Is 2 s. ) .01213017 -10 -10 -11 204 -171 11164 -10020
A A
(Is, 2 s/ls, Is ) .00002883 0 0 0 0 0 -1 -1
A A
(2 s 2s /Is,2 s, ) .05790995 0 6 -7 -405 -7 -4485 -4797
A A
(2 sa 1 sa/2 s 1 sa) .00718061 0 6 -1 -46 -1 -1450 -4482
(2 s, 2 s /2 s, 2 s,) .23550407 0 0 0 -334 0 118 118

(Is, ls,/2 s, 2 s,) .00774155 0 0 0 0 0 3 4
.25849801 0 0 0 0 0 0 -1
(2sa 2 sa/2sa 2 sa)
64
TABLE VII
K-CONVERGENCE TESTS
K-quadrature schemes are of Che composite Gauss Legendre form,
Equation (37).
(0., n^, .8 n£» .91, .96, n^,, .985) ** (n^, nj, ^3 *
Here only one subinterval Is UBed and the nodes are specified with each
table.
A 32
B 28
C 24
D 20
E 16
F 12
G 8
H 4
I (20,5,36)
u-Quadrature Scheme
K-Convergence
Integral Block (lsyls^/ls^ls^)

D(K) - 1(A) - I(K) K ** B,C,D,E,F,G,H,I
Comparison
Value
Integral Block A B C D E F G H I
K Quadrature (0.,n,.8)
(c c / c ^ ) 1.09450882 0 0 0 0 27 794
(c c /c2 c2) .49865412 0 0 0 0 -461 108237
(c c /c3 C3 ) .32354537 0 0 0 -62 9678 -679890
(c c /c^c^) .25708544 0 0 -6 835 -67140 2112327
(c C / Cj-C,-) .19777977 0 0 65 -5360 301916 -32084251
(c C /CgCg) .16599751 0 4 -321 25050 -996172 9448
K Quadrature (.8,n,.91)
(c C / C jC ^) -.08420040 0 0 0 0 0 24
(c c /c3 c3) .00932516 0 0 0 0 67 67279
(c c /cAcA) -.00644003 0 0 0 1 114 376094
(c c /c5 c5) .00176262 0 0 0 -125 -42315 -1392920
(c c /c6 c6) .00136778 0 0 5 2519 175581 -2056770

K-Convergence
Integral Block (ls^ls^/ls^ls^)

D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
Integral Block A B C D E F G
K Quadrature (.91:
,n,.96)
(c c / c ^ ) .00109383 0 0 0 -1 -1266 31979
(c c /c3 c3) .00047423 0 0 -2 -1260 -77348 -28669
(c c /c4 c4) -.00064467 0 10 616 -54220 182705 203961
(c C / C ^ C j) .00045388 17 1935 10311 -31959 7665 19559
<c c /c6c6) -.00020111 752 36976 -84052 -109475 -57526 -67123
K Quadrature (.96 - .985)
(c C /c^Cj) .00001669 0 0 0 -13 402 -5985
(c C / c 3c 3 ) -.00000877 -74 435 -1179 358 -3987 -2440
(c c /c4 c4) .00000602 421 2299 -2075 2506 1391 -1148
(c C /C j Cj ) .00000803 -77 240 2102 2731 3241 393
(c c /c6c6 ) .00001450 2883 1701 1031 1782 5037 -519

K-Convergence
Integral Block (ls^ls^^/ls^ls^) K Quadrature (0 - .8 )

D(K) = 1(A) - I(K) K = B,C,DfE,F,G,H,I
Comparison
Value
Integral Block A B c D E F G H I
(c c /c c1) .50687938 0 0 0 0 0 28331 -16547
(c c / c ^ ) .41707527 0 0 0 0 0 100330 1205
(c C /Cj Cj ) .31597928 0 0 0 0 0 56912 343
(c C /c3 c^) .24071174 0 0 0 0 70 -91182 -311
(c C / c^c5) .19022705 0 0 0 3 -1176 -1097522 46
(c c /c5 Cg) .15615558 0 0 0 -59 3055 1414561 96
(c .39532798 0 0 0 0 0 5082 -2778
(c c^/c^) .31118396 0 0 0 0 0 265825 17
(c .23602178 0 0 0 0 30 247724 65
(c cx/c4 c5) .18310131 0 0 0 1 -335 -5326321 0
(c c1 /c5 c6) .14755465 0 0 0 -21 -333 -194941 -22

K-Convergence
Integral Block (ls^ls^/ls^ls^) K Quadrature (.8,n,.91)

D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
Integral Block A B c D E F G H
(c c /c1 c2) -.00001204 0 0 0 0 0 0 1
(C C /CjC-j) -.00000344 0 0 0 0 0 0 -56
(c c /c3 c^) .00000311 0 0 0 0 0 -3 -181
(c c /c4 c5) -.00000048 0 0 0 0 0 -33 -134
(c C /CjCg) -.00000094 0 0 0 0 2 -80 54
(c c /C6C7> -.00000359 0 0 0 -1 77 -596 1739
(c c1/c1c2^ .00002772 0 0 0 0 0 0 -3
(c c^/c^) -.00000017 0 0 0 0 0 0 -28
(c c1 /c3 cA) -.00000066 0 0 0 0 0 0 -41
(c ^ / c ^ ) .00000000 0 0 0 0 0 -5 -25
(c c1 /c5 c6) .00000003 0 0 0 0 0 -19 -11
cr>
oo
K-Convergence
Integral Block (lSjls^lSglSg) K Quadrature (0,n,.8)

D(K) « 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
(c c /c.jC2) .19884926 0 0 0 0 0 -3251 -1204
(c c /c2 C3 ) .13607613 0 0 0 0 -10 -34021 5829
(c c /c3c .07939026 0 0 0 -1 19 426221 -2236
(c c /c^c5) .07755949 0 0 0 13 1153 -104265 *499
(C C /CjCg) .06397371 0 0 1 -64 -11470 -103711 1333
(c c /c6 c7) .05367031 0 0 -15 -76 45201 • 574018 -889
(c c /c7 c8) .04651023 0 -1 84 2745 -65427 -96463 14
(C C /CgCg ) .04103364 0 13 -266 -16056 -70141 -820161 357
(c c /c,c10) .03670070 1 -71 93 46384 311445 -340494 -505
(C ^ / C g C g ) .03745190 0 2 64 -6489 -98392 -461371 -144
.03328122 0 -11 -606 9883 129376 -555252 44

(c cl/c9c10)
O'
VO
K-Convergence
Integral Block (lc^c / c ^ ) K Quadrature (Ojn, .8 )

D(K) = 1(A) - I(K) K « B,C,D,E,F,G,H,I
Comparison
Value
(lSjlS^lSj.lSj.) .19022905 0 0 0 3 -1176 46
(ls1 ls1 /ls1 ls3) .09189992 0 0 0 45 -2525 -1636
(^^/lsjlsj) .19104738 0 0 0 55 1525 342
(^ls^yls^^) .09178649 0 0 -2 65 21422 -20469
(ls^ls^/lsj^^) .09163358 0 0 0 -252 36960 -40525
(ls7 ls7 /ls1 ls7) .03048253 0 0 6 -544 34499 -59119
(ls7 ls7 /ls,ls,) .07746393 0 0 4 -448 23649 -20004

K-Conve rgence
Integral Block (c c^/c^c^) K Convergence (0,n,.8)

D(K) = 1(A) - I(K) K « B,C,D,EtF,G,H,I
Comparison
Value
ntegral Block A B C D E F G H I
lS j^ S j/ lS jlS j) .18310131 0 0 0 1 -335 0
Is Is^/ls^ls^) .03651150 0 0 0 -1 61 -364
.04846580 0 0 0 -15 1707 4175

lslls3/lslls3)
ls^ls^/ls^ls^) .04237881 0 0 0 30 4046 -2637
ls^ls^/ls^lsy) .00470610 0 0 0 -54 3965 -5173
ls1 ls1 /ls1 ls7) .00584677 0 0 0 6 -772 7296
K Quadrature (.8,n,.91)
.00000000 0 0 0 0 0 -5 “25
lsllsl^lsllsl^
lS jis y iS jiS j) .00000639 0 0 0 0 0 -9 -631
lsjls^/lsjls^) -.00004174 0 0 0 0 0 -94 -3213
lajsjlafaj .00002591 0 0 0 0 3 -467 -81
Is Is /Is Is ) .00004175 0 0 0 0 -90 -3298 -9685

7 1 1 7
Is Is /Is Is ) -.00007319 0 0 0 0 -5 -56 -16878
1 7 1 7
ls3 ls3 /ls3 ls3) -.0000*303 0 0 0 0 -4 238 -597
K-Convergence
Integral Block (c c ^ / c ^ c . ^ ) K Quadrature (.8,n,.91)

D(K) = 1(A) - I(K) K = B,C,D,E,F,G,H,I
Comparison
Value
Integral Block A B C D E F G H
( l S j l S j /l S jl S j) .00000023 0 0 0 0 0 -19 -11
(ls1 ls7 /ls1 ls1) .00000037 0 0 0 0 0 -218 -479
(^^/ls-jl^) .00001960 0 0 0 0 3 -713 -4192
(ls3 ls1 /ls1 ls3) -.00001787 0 0 0 0 63 -1037 5422
(ls7 ls1 /ls1 ls7) -.00000443 0 0 0 5 490 -7720 16358
(Is Is /Is Is ) .00002540 0 0 0 0 -37 -5803 -12965

1 7 1 7
(1 e 3 1 s 3 / 1 B 3 1 s 3 ) .00002451 0 0 0 0 -22 -20 -2598
73
TABLE VII Contd.
K-CONVERGENCE TEST
u - Quadrature 12. 24, 12
K - Quadrature
A ( 0, 32, .8 , 32, .91, 32, .985)
B (0, 20 , .80, 20, .91, 20, .985)
C ( 0 , 16, .80, 16, .91, 16, .985)
D (2 0 )
E (28)
F (36)
G (35/64)
H (16, 5, 24)
I (20, 5, 36)
Integral Block (c cj/c2c^
Differences from comparison value In 8 th place where difference Is
D(K) = 1(A) - I(K) K » B,C,D,E,F,G,H,I
Comparison
Value
Integrals A B c D E F G H I
(ls^lSj/lSjlSj) .31118378 0 0 179 10 4 0 0 0
(ls7 ls7 /ls1 ls1) .00904316 0 0 -6 0 0 0 0 0
(lS^lS^/lS^lSy) .02199311 -3 -3 2480 -115 -15 0 -42 3
(ls7 ls7 /ls1 ls7) .00140036 0 1 -88 51 -14 0 -4 1
(lS^lS^/lS^lSg) .14042465 0 0 “171 7 0 0 0 0
(ls3 ls3 /ls3 ls7> .01843082 -1 0 850 18 -22 0 2 -16
(lsllsi/ls7 lsl) .07293664 0 0 -45 2 0 0 0 0
(ls7 ls7 /ls7 ls1) .00219857 0 -1 8 0 0 0 0 0
(ls7 ls7 /ls7 ls3) .00159889 0 0 0 0 0 0 0 0
(ls7ls /ls7 ls7) .00025277 0 0 -19 2 0 0 0 0

Integral Block (c c /
Differences from comparison value In 8th place where difference is
D U ) = 1(A) - I(K) K = B,C,DtE,F,G,H,I
Comparison
Value
Integrals A B C D E F G H I
(IS^lSj/lSjlSj) .41706322 0 0 -247 25 1 0 0 0
(ls7 ls7 /ls1 ls1) .49852768 -1 -15 -220 18 -1 0 -4 1
(lSglSg/lS^Sy) .07880811 -13 -101 -96 49 -5 3 -25 6
(lSylSj/lS^lS^) .07883472 -159 -1645 3998 743 -121 84 -547 143
(lS^S^lSglS^ .19885951 0 0 -112 5 0 0 0 0
(ls3 ls3 /ls3 ls7) .06714346 0 -80 181 24 -3 2 -21 4
(ls1 ls1 /ls7 ls1) .10497530 0 0 -24 1 0 0 0 0
(ls7 ls7 /ls7 ls1) .14244517 24 4 39 2 0 0 0 0
(ls7 ls7 /ls7 ls^) .10082343 25 29 117 -1 0 0 -2 0
(ls7 ls7 /ls7 ls7) .01513811 26 -53 591 -23 -2 3 -25 5

76
Computing Integral Blocks
The Integrals to be computed are specified by the centers of
the orbitals. These give sets of p-vector generators, i.e., the
vectors r , r , and r , and are referred to as integral blocks,

ab cd ac
All integrals in a block are to be computed using the same quadrature
scheme.
As discussed in the previous sections, different Integrals
in the same block may not need very different quadratures for their
evaluation. The quadrature scheme for the integral block must satis
factorily treat all of the Integrals; this usually results in over
computation of moBt of the Integrals within a given block. Neverthe
less, it is generally considerably more efficient to compute the entire
block together than to compute subblocks using their optimum quadra
tures. The reason for this is that the computer routines which we have
developed are very efficient if large numbers of Integrals use the same
F-matrix; it is the evaluation of the different coses of the F-motrix
that Is the time consuming step. Unless large subblocks requiring
significantly different quadrature can be defined, the integrals in the
block should continue to be treated together, i.e., for some large
blocks we should treat the K and L shells separately.
Testing
The s and p portions of the routines have been extensively
checked with Hagstrom's programs. Multicenter d integral values were
not available from his calculations and other methods have been used
to verify the routines.

TABLE VIII
Comparison of ERIC* with Gaussian Expansion Method**
INTEGRAL BLOCK (CiC2 /CiC3)
Centers
Ci 1.0 -1.73205 1.0
C2 0. 0. 0.
C3 0. 0. -2.30
Orbitals
Is 1.2
d 1 .
p 1.625
*ERIC - Fourier transform method programs developed in this work:
K-Quadrature (32,5.,36)
U-Quadrature [12,24,12]
**IntegralB evaluated using GINT by Sasaki, F.

Least square expansions obtained using GAUSFIT.
78
Integral Block (Is ls/ls Is) Comparison Value: .025325A6
Integral Value (times 101)
Weighting Function
Rank r~*
r“ 2 1 r
3 .196352A35 .2AAA17A5A .2533933A6 .25312373A
A .2378A21A7 .252962259 .253A09267 .253012596
5 .250206967 .253A2A7A3 .2531710A9 .25322AA51
6 .253010326 .2532181A6 .2532A1626 .2532552A3
7 .253318322 .253216065 .253262255 .253250067
8 .2532A0919 .25325156A .253255702 .253253568
9 .253217635 .253258AA7 .25325367A .25325A703
Integral Block (3d ls/ls Is) Comparison Value: -.01353858

xy
Weighting Function
Rank r
rll 1 ^. 1
3 .109127090 -.13103A632 -.135A6A578 -.1351606A0
A .128083A73 -.135261292 -.135A12A18 -.135220873
5 .13393861A -.135A31A5A -.135352632 -.135365106
6 .135239795 -.135363969 -.135380A37 -.133557257
7 .135389259 -.1353699A1 -.135388A63 -.135383155
8 .135371051 -.13538A26A -.135386177 -.1353851A3
9 .135369A62 -.135387068 -.135385A68 -.135385733

79
Integral Block (3dv„
xy ls/3dvv
xy la) Comparison Value: .01469001
_______Weighting Function
lank
r" 2 Hi 1 r
3 .143607066 .147022573 .146953014 .146508865
4 .146708877 .146989420 .146868291 .146794859
5 .146996529 .146893816 .146901578 .146881613
6 .146939461 .146897021 .146898883 .144867314
7 .146904126 .146898854 .146900158 .146898311
8 .146897298 .146899955 .146899951 .146899620
9 .146898934 .146899940 .146900117 .146899943
Integral Block (3dxy ls/3dyz Is) Comparison Value: .03029388
_______Weighting Function
lank
r- 2 Hi 1 r
3 .312749080 .305764594 .303147557 .301973811
4 .307120938 .303303570 .302836305 .302684354
5 .304107200 .302909512 .302946679 .302889024
6 .303169457 .302929412 .302934539 .299098321
7 .302955920 .302934801 .302938234 .302934077
8 .302928863 .302937364 .302938149 .302937374
9 .302934810 .302937790 .302938685 .302938233

80
One and two center integrals can be accurately computed using
other methods and thus provide a useful check. The integrals may also
be treated as multiccnter integrals, thus providing a further check.
The multicenter d integrals were tested by using least square
gaussian expansions for the Slater orbitals and evaluating the integrals
over the gaussian orbitals. Gaussian expansions of rank three to nine

28
for various weighting functions were obtained using Gausfit. Several
test cases are given in Table VIII along with the results of the present
work.
Capabilities and Performance of the Integral Routine
The programs that we have developed provide a general and effi
cient procedure for the computation of molecular repulsion Integrals.
The routines will compute all of the two electron coulomb, hybrid and
exchange integrals over cartesian Slater type orbitals with £ <^ 2. In
addition, the one electron nuclear attraction integrals are treated as
a special case of the hybrid integral.
As previously discussed the accuracy and computation time for
the integral evaluation are determined by the quality of the quadrature
scheme involved. In general, we have that as the number of orbitals
Increases, the routines become very efficient. The programs have been
designed such that, to within core restrictions, the quadrature schemes
are open ended. In principle, any desired accuracy may be obtained. In
practice, we have found that six digit accuracy may be obtained, even
for highly asymmetric charge distributions.

81
The computation times for the evaluations of several blocks of
molecular repulsion Integrals Is given In Table IX. It Is Important to
emphasize that the routines are not optimum for computing one and two
center integrals. Algorithms specifically designed for these integrals
are available which are on the order of 100 times faster than the routines
developed here.^
TABLE IX
CALCULATION TIMES (CDC 6600)
BENZENE
For Integral block (CjC2 / CjC3)

Using [8 , 16, 8 ] u,v quadrature scheme
(36) k quadrature scheme
Accuracy — 6 digits
Calculation Time (Seconds / Integral)
Basis Size S Orbitals F Orbitals

x
2 .22 .506
4 .0461 .1035
6 .0227 .030
8 .0138 .0272
9 .0126 .0169
00
ro
BENZENE For Integral block (CjC3 / CgC^)
u,v quadrature [8, 16, 8 ]
I. DOUBLE-ZETA BASIS -- 5648 non-zero Integrals
K-Quadrature Computation Time Time/Integral Accuracy

(Seconds) (Sec./Integral)
(32) 389 .069 6 - Digit
(16, 5, 20) 642 .11 6 - Digit
(16, 5, 24) 700 .12 8 - Digit
(20, 5, 36) 809 .14 8 - Digit
6S, 2P ON EACH CENTER -- 12,416 non-zero integrals
K-Quadrature Computation Time Time/Integral Accuracy

(Seconds) (Sec./Integral)
(20, 5, 36) 985 .079 8 - Digit

BENZENE III. Id ON Cx AND AS, 2P ON C2 , C 3 AND K-Quadrature (20, 5, 36)
Integral Type Number of Integrals . Computation Time Computation Time

(Seconds) (Per/Integral)
A) (ds/ss) 192 35 .18
B) (ds/sp) 512 1A3 .28
(ds/ps)
C) (ds/pp) 368 192 .52
D) (pd/ss) 992 759 .77
(pd/sp)
(pd/ps)
E) pd/pp 678 1197 1.77

CALCULATION TIMES (CjH)
Integral Blocks
(HC! / C^Cj) Using [8 , 16, 8 ] u,v quadrature scheme
(HC2 / CiC2) (36) k quadrature scheme
(HCj / HC2)
Basis # Nonzero Integrals Time (Seconds) Sec./Integral
Minimum 101 36.9 .365

Double-Zeta 1616 78.A .0485
Triple-Zeta 7695 250.8 .0326
Integral Blocks (Double-Zeta)

(C1 C1 / hc2) 532 Integrals .010 Sec./Integral
(HH / CjC2) 132 Integrals .0443 Sec./Integral
(C C / C C ) Calculation Time - 100 Seconds

1 2 1 2
Using Deric* ** 7 Seconds
Total Integral Time for Double Zeta C2H = 150 Seconds
*Deric - 2 Center Program, QCPE 252 by S. Hagstrom
CD
wt
COORDINATES
Centers
1 . -1.73205 1.
0 . -1.73205 1 .
0 . 0.00000 0 .
0 . 0.00000 -2.3
u,v - quadrature (8 , 16, 8)

k - quadrature (36)
Integral block (CjC2 / C^C^)

Basis set C : Is, Id
1
<^» Q* : Is, lp
Integral Type Number of Integrals Computation Time Computation Time

(Seconds) (Per Integral)
(ds/ss) 5 6 1.2
(ds/sp) 30 38 1.28
(ds/ps)
(ds/pp) 45 111 2.47
(dp/ss) 15 23 1.53
(dp/ps) 90 216 2.40 os

Co
(dp/sp)
Integral Block (C^Cj/ C3C^)
Integrals (ss/ss) (ds/ss)

(ss/sp) (ds/sp)
(ss/ps) (ds/ps)
(ss/pp) (ds/pp)
Basis Number of Integrals Computation Computation Time

Time (Per Integral)
A) : Is, Id 80 84 1.05
C1
: Is, Ip
C2 * C3’ C4
B) : Is, 2d 352 186 .53
C1
: 2s
C2
: Is, lp
C3* C4
C) : Is, 3d 512 211 .41
C1
: 2 s.
C2
c4 : Is, lp
V
D) : Id 960 152
C1
: 3s
C2
c3 , C4 : 2 s, 2 p
□a
-s i
Integral Block (C^Cg / C ^ ) - Contd.

Time (Per Integral)
E)* C, : Id 1560 208 .13
: 3s, lp
• 4s, 3p
: 2 s, 2p
F)* C, : Id 192 76 .13
: 3s
: Is, lp
C3* C4
Integral Block / C^C^)

(sd/sd) integrals
Basis Set - C_ C. : Is u,v quadrature 12, 24, 12

2 4
k quadrature (36)

Time (Sec.) (Per Integral)
FOR C,
2d 100 127 1.27
3d 225 157.4 .70
5d 625 189.5 .30
*(ss/ss), (ss/sp), (ss/ps), (ss/pp) not included

89
APPENDIX A
GAMMA MATRIX
The gamma matrix which specifies the general d type Slater orbitals
is defined in Table I as
a , a
Wj *Stil2
a a a
'a
^ 3 hv* 3m?
If we restrict the one electron basis to canonical orbitals, then the
set of allowed y matrices is limited. The gamma matrices that result
from the canonical d orbitals and products of y's are listed below.
There is at most two nonzero elements per matrix and only the nonzero
elements are given. In addition, each nonzero element is taken to be
either - 1 ; the constants.in the canonical y's are included in the
normalization. The canonical d orbitals correspond to the following
matrices.
nd 2 2 " Y„
'9
nd 9 9
x ~y '18
nd Y 12
xy
j
nd
xz
3 Y13
nd » y,-
yz '15
In the table we list the indices of the nonzero terms. A positive
term indicates a +1 and a negative index represents a -1. For example,
Y 16 has the nonzero terms -1 , 2 , and 2 , 1 .

90
0 - 1 0
1 0 0
*16
0 0 0
The product w^Yj occurs frequently In the calculation. When
canonical p orbitals are used, we have
w (1,0,0) wy - (0 ,1 ,0 ) wz ■ (0,0,1)
The product w^Yj then has at most one nonzero term which Is - 1; the
nonzero terms are also given In the following table.
TABLE X
Y MATRICES
Nonzero Trace Transpose u y. WyYj1 uzl

Y1
Term x' 1
1 1,1 1 1 1 0 0
2 1,2 0 A 0 2 0
3 1,3 0 7 0 0 3
4 2,1 0 2 0 2 0
5 2,2 1 5 0 2 0
6 2,3 0 8 0 0 3
7 3,1 0 3 1 0 0
8 3,2 0 6 0 0 3
9 3,3 1 9 0 0 3
10 1 »1 ;2 , 2 2 10 1 2 0
11 i,i;3,3 2 11 1 0 3
12 1 ,2 ;2 , 1 0 12 2 1 0
13 1,3;3,1 0 . 13 3 0 1
14 2,2;3,3 2 1A 0 2 3
15 2,3;3,2 0 15 0 3 2
16 -1 ,2 ;2 , 1 0 -16 -2 1 0
17 -2 ,2 ;1 , 1 0 17 1 -2 0
91
TABLE
MULTIPLICATION TABLE FOR y MATRICES
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
1 1 2 3 0 0 0 0 0 0 1 1 2 3 0 0 -2 1
2 0 0 0 1 2 3 0 0 0 2 0 1 0 2 3 1 "2
3 0 0 0 0 0 0 1 2 3 0 3 0 1 3 2 0 0
4 4 5 6 0 0 0 0 0 0 4 4 5 6 0 0 -5 4
5 0 0 0 4 5 6 0 0 0 5 0 4 0 5 6 4 -5
6 0 0 0 0 0 0 4 5 6 0 6 0 4 6 5 0 0
7 7 8 9 0 0 0 0 0 0 7 7 8 9 0 0 -8 7
8 0 0 0 7 8 9 0 0 0 8 0 9 0 8 9 7 -8
9 0 0 0 0 0 0 4 5 9 0 9 0 7 9 8 1 0
10 1 2 3 4 5 6 0 0 0 10 1 12 3 5 6 ■16 17
11 1 2 3 0 0 0 7 8 9 1 1 2 13 9 8 -2 1
12 4 5 6 1 2 3 0 0 0 12 4 10 6 2 3 17 16
13 7 8 9 0 0 0 1 2 3 7 13 8 11 3 2 -8 7
14 0 0 0 4 5 6 7 8 9 5 9 4 7 14 15 5 -5
15 0 0 0 7 8 9 4 5 6 8 9 7 6 15 14 7 -8
16 4 5 6 -1 -2 -3 0 0 0 16 4 ■17 6 -2 -3 •10 2
17 1 2 3 -4 -5 -6 0 0 0 17 1 •16 3 -5 -6 ■12 10
92
APPENDIX B
The parametric differentiation formulas indicated in Equation (17)
are easily derived using the following relations.
1> D > nCO- -r+b V l <.)
2> !a+!ab " 1
3) ? a V a b - r“
ri I
4) i U (z) - So a U (z) - uD .,<z)
a n' ' a a n n+ 1
+ , <kp)
5) Do+ ^ kP> - (l-u)5 + jjp
p
*4* *4*
6> ?b“n ' !ab Un-1

7) Db+ i / kP> - us
■r •
8> ”b \ rab--rz
9) ^ U n (z)--Sob ^ Un (z) - (l-u)Un+1 (z)
10)
45o Un Cz) ■ - uoaUn+M1 '
(z)
aa
u) L \ M - Vfi - (l-u)obUn+1 (z)
b “b
Where
+ 1 - i
Da - a* Sya ’ Sza
+ (*■ 1 1 )
Db ' 5xb> 5yb> 5V
i £ £
6P " (6px * 6py ' 6pz *
ag, are the orbital exponents.

93
-1
Derivation of the Formula for the (3d Is, / r,„ /Is Is,) Case
a d iz c Q
Using Equation (8 ) and Equation (15), we have
I - (3dal9]) / r1 2 _ 1 / lscl8 d) - A(3da)(l9 alsb / r12-X / 1^1*,)
- A(3dfl) 8 , J ik j duu(l-u)U3 (u,k) / dv(l-v)V3 <v,k)f0 (kp)
The A (3d ) parametric differentiation operator is given in Table I as
A (3d ) » (wa a2 + D +Y D ) l z - 2 u * f 2
a o a .a La.a a 0 6 or
We may thus write I as
I ■ 8 7rJ dk j dw(l-v)V^(v,k) j duu(l-u) (A(3da)U3 (u,k) (^(kp)}
Therefore, we need to evaluate
A(3da)(U3 (u,k),{0 (kp)
■ [(u a2 + D y D )-£2 — 2wa TTT ] U_(u,k) (5«(kp)

0 a a a a a 0 ocx*- J J u
^
2uq !l, 11,4, - I 6 m , X - 2u2r“us ) <„

5az
a
£2U (u,k)/ (kp) - u2Us (u,k) (J (kp)

a 3 uo 0
Da V a V u-k> « <kp)
«* •> % *
- Da+Ya t -aU^(u,k) fSg(kp) + (l-u)$pU5 (u,k) li0 (kp) ]

*■ *r ■»
- { rau 3 (u,k) - [ 2(i-u)rJ + rf ]u^(u,k) + (i-u)2r*u5 (utk)} rf0 (kP )
Therefore
u 2rau + u(6uj-ur|)u1(-u2rjus + ll
1 3
A(3da)U(u,k)^(kP) -2 u2 (1 -ujU^ K
u2 (l-u)2 U5
r
94
and
I - (3dalsb / r-J / lsclsd)
-6* / d k / " duu(l-u)U+ (3da lsa ) r (3da lsb ) j dw(l-v)Vj(v,k) <0 (kp)
APPENDIX C
Derivation of the F-Matrlx Formulas
The F-matrix is defined by Equation (19) as

p(u,v,k) a ( u)r(v,k), (kp)
*ijkl ij v.u,k;i ^ A0
where the T's are the corresponding charge distribution operator
matrices defined by Equation (17). Each of the elements of the matrices
is a product of the operators,
r* * W
■v
a ■'
-
p
5 „p,a„p
rA - (0.6
7 A p
rAS - (o.yn6
9 A'B p
*w *m
The derivation of the F-matrix formulas therefore only involves the
indicated derivatives. For convenience, a few of the necessary terms
are included below.
Operator* (Times f^(kp))
21 *
r 7h
r \ b u .r + r r rz
7 7 ab 7 7
J ,
—C _J) an - n - K - p . 3
"bcr7 + wabr7 + w acr7)R + r7 r7r7R
rarb7i7i7
i7i rcrd (u , (i) , + (i) j W . + w u». ,)R2 + [ f7 (w jf-
' ab cd ad be ac bd 7 cd 7
96
r? rfii + rfe2
rfrf* <r?r£ + 2rf>it2 + (r?r| + ffb + rfb+ + ra+b
+ r|rf + f | ^ +)Rs+ ffr^R1*
- <rfr£ + 2r|b)R2 + (F|rb + «Ffb + F^|) r 3
+ rfr^R"
I£ ifa - lfa+
fb ” *b+
rfrsrs - [ rj(rbrf + 2rab) + 2rfrfb + a r ^ 1’ + 2rbrja] r3
+ [<rbr“ + 2 r f > r ^ + ( r br“ + 2 r ab)Fa
+ (r£r£ + 2r|c)fb + 4(F^bra + rfbrf + F^rJ)
+ 8(rfba + rgab + racb) 1 i- + [ i'bF|F?
+ r2?5F5 +r2?5?5 +4< ???' + F“ Fb

+ FsbF?>]R5 + F5F5F5R6
Y iYt tY Symmetric
'a b 'c
_ba
5 7 (2Fab + rbra)R2+ FbFaR3
r “r ^ »?? * + +
+ r^FjF, + F‘ „ ac)R3 + F“ FfF,R-
r 5r5r7 + *?frj + + «?,cbd
,.-cdb , „„d-cbs ^ 3 , ,-d-c b , .-bd-c

+Ars + 2r2r9 )R* + (r5r 7r2 + 4r5 r 7
+ rM f? + 2F9drt + 2FsFfb)R*«
+ r^rdr5 R5
97
The constants are defined in Table II and the F's are related to the
1 operators by replacing the differential by the vector p.
fj
" rabYAP
n ■ ?ya f
$ A
■ “aV
* The F operators all commute* i.e., rgr7 ■ ^7 ^ 5
** The y matrices for the cononical orbitals are all symmetric but the
products YqY|j are general not symmetric.

98
I
REFERENCES
1. Klahn, B. and Bingel, W. A., Theoret. Chim.Acta (Ber.) 44, 27

Int. J. Quan. Chem. II, 943 (1977).
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Shavitt, I., Chem. Phys. Lett. T_y 325 (1970).
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Bibliography of ab initio Molecular Wave Functions, Supple
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213 (1973).
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Chim. Acta (Berl.) 4E, 59, (1978).
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11. Salmon, L. S., Blrss, F. W. and Ruedenberg, K., J. Chem. Phys. 49,
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Salmon, L. S., Int. J. Quan. Chem., _7, 411 (1973).
12. Wahl, A. C. and Land, R. H., Int. J. Quant. Chem., Is, 375 (1967).
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Energy Surfaces in Chemistry, Lester, W. A. (Ed.). IBM
Research Laboratory, 1971.
13. Chang, S. J. Comp. Phys. .20, 243 (1976).
Haselegrove, C. B., Math. Comp. 15, 323 (1961).
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37, 275 (1975).
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3083, 40, (1964)
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100
17. Rees, D., Deborah, J. M.» and Taylor, P. R., Theoret. Chim. Acta (Berl.)
31, 183 (1973).
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Academic Press, Osgood, C. P. (Ed.), 1973.
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3083, 40 (1964).
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_7, 233 (1973).
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Academic Press, 1975.
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THE GEMINAL MODEL
101
In principle, the usual methods of quantum chemistry are capable
of providing an exact solution of the molecular electronic Schrodlnger
equation. All of the chemical information available would be present
in the computed wavefunction, but in an extremely inconvenient and
inaccessible form. We thus propose model approximations which make
simplifying assumptions about the nature of the system. We assume or
hope that the model is reasonable and tractable so that it lends
Itself to an analysis and understanding of the system.
The most common model approximation made in quantum chemistry is
the independent particle or the Hartree-Fock self-consistent field
model.^ This model has proven very useful and has had a profound
2
effect on the woy we look at chemistry.
The model, however, is incapable of describing the correlation
associated with the mutual repulsion of the electrons and cannot
describe certain chemical behavior, e.g., it does not lead to an

3
adequate description of bond dissociation. A generalization of the
HF-SCF model which accounts for at least part of the electron
correlation is thus needed. One possible generalization is to introduce

4
the chemist's concept of electron pairs. In closed shell HF-SCF
theory, each pair of electrons is described as a single pair of spin
orbitalB. A generalization of the theory would be to describe each
pair by a linear combination of spin orbital products. That is, we
wish to approximate the electronic wavefunctlon as an antisymmetrized

5
product of pair functions called geminals.
102
The Geminal Model
We approximate the electronic wavefunction for a 2N electron
system as a simple antisymmetrized product of tvo electron functions
or geminals, the APG model.t
*APG " 6slA * A (2u-1,2 p) (1)

II-1 M
A A
where A is the partial antisymmetrlzer, is the appropriate
projection operator and the A *s are the geminals. We require that

P
the geminals be antisymmetric
A.^1,2)— A ^ . l ) (2)
and normalized.
//dTldT,A*(l,2)A (1,2)-1 (3)

1 2 y p
General expressions have been derived for compilation of the

g
Hamiltonian and overlap matrix elements over geminal functions. In
general, these expressions have proven to be too formidable for actual
computations and APG calculations have only been performed for certain
7
A electron systems. To obtain a more tractable formulation, it is
necessary to make simplifying assumptions.
The assumption that the geminals are strongly orthogonal
^Generalization to systems with an odd number of electrons are straight

forward. Each pair of electrons is described by a geminal and the re
maining electron is described by a single orbital with a spin.
103
leads to rather simple expressions for the energy expectation value.

q
Most geminal calculations performed have required strong orthogonality.
Antisymmetrized products of strongly orthogonal geminals are usually
referred to as separated electron pair functions, SEP.
The strong orthogonality condition, however, Is an arbitrary
constraint and Is, In general, too restrictive. It 'significantly
reduces the usefulness of the model but, In general, Is necessary for
a tractable formulation.
Several authors have considered generalization and extensions of
the SEP and APG models. Silver Introduced the idea of Interacting
geminals.The natural orbitals (NO) of the geminals are required to
be the NO's of the wavefunction but the geminals are not required to
be strongly orthogonal. McWeeny generalized the concept of an anti
symmetrized product of pair functions to an antisymmetrized product of
group functions.^ In addition, several authors have generalized the
APG functional by considering the wavefunctions consisting of linear

12
combinations of APG functions. In general, however, these models
have proven to be computationally inconvenient and have not been used.
In this work we are primarily concerned with the development of
a general procedure for computing SEP wavefunctions. In particular, we
shall examine the applicability of the generalized Brillouln theorem.
We shall then examine the feasibility of using this procedure for
computing APG wavefunctions.

The Separated Electron Pair Model
We are concerned vlth approximate wavefunctions of the form
“ A tt A (2y-l,2y) (5)
P=1 W
where the geminals, Ay, are required to be antisymmetric, orthonormal
and strongly orthogonal — equations (2), (3) and (A) describe these
conditions. We can expand each geminal in terms of 2 by 2 Slater
determinants formed froma complete orthonormal set of spin orbitals.
n (1 ,2 ) - 2 cN [ t M D M 2 ) - iM 2 ) M i) ]//T “ (6)
V i<j ij J
By using the natural spin orbitals (NSO's) obtained by dlagonallzing
the first order density matrix, this expression may be reduced to a

^ i sum. 1 3
single
n (1,2) - E C [X (1) X (2) - X (2) X (l)]//2“ (7)

v 1 Pi 21 -1 21 21-1 21
The normalization condition, equation (3) gives the occupation numbers,
c^, the property
Ec -1
1 yi
The condition that the geminals be strongly orthogonal requires that
we expand each geminal in a mutually orthogonal subspace of the
orthonormal orbitals, Aral's t h e o r e m . T h a t is, for strongly
orthogonal geminals A^ and A^ expanded in terms of natural orbitals,
we have
S ^ l ^ - ^ l " 5 MN5kl
105
We, therefore, have that, for the SEP wavefunctions, the NSO's of the
geminals are also the NSO's of the wavefunction ij/ •
In order for the total wavefunction to have a specified spin and
spatial symmetry, we require that the geminals be eigenfunctions of

2
S and Its z component, S and that they be symmetry adapted. The
z
natural expansions then assume different forms In the singlet and
. , cases. 1 5
triplet
S-0 nN(l,2) - EC * U)*j(2)[a(l)B<2)-B(l)a(2)]/i/r (8 )

j
a(l)a(2 ) M - 1
s
;-l f!H(l»2) - EC [x.(l)y.(2) - y (l)x, (2)] J [a(l)B(2) + B(l)o(2)]//T
N j N J j j j J 1 M-l
s
B(l) 3 (2 ) Ms — 1
106
Energy Expressions
The nonrelatlvistic electronic Hamiltonian for the 2N electron
system is
H " E h. + E r
i 1 1<J 3
where
h — \ V .2 - Z Z r ~.1
i 2 i a a ai
The labels i,j and a,0 indicate electrons and nuclei, respectively.
ZQ is the charge on nucleus a.
The energy expectation value is easily derived using the orthogonality

16
relations, equations (2), (3) and (A). If we define
E(u> - // d Tj d T j A *( 1 , 2 ) ^ + h2 + i \ Au( l , 2 )
and
I(u*v) ■ A J(u,v) - 2k(u,v)
with
J(u,v) - ////A*<1,2)A*(3,A)A-A (1,2)A (3,A)dT1 di_dT.dT

h v r^j y v i L j 4
and
* p
K(u,v) - // // dTjdx^d^ Ay (l,2)A*(3,A) ^ A^(l,2)Av(3,A)
then the energy expression is given by
E - E E(u) + E<v I(u,v) (9)

107
The terms In the energy expression may be given a simple physical
interpretation; E(u) represents the energy of geminal u In the field of
the nuclei, and I(u,v) gives the interaction energy between geminals u
and v. We can define the total energy of the geminal u within the
system by
Eu - E(u) + I(u) (10)
where
I(u) - I(u,v)
It is then possible to express the total energy as
E ■ n u - E I(u,v)
u u u<v
and
E - y E (E(u) + Eu}
The significance of these equations has been discussed by Shull and

17 18
co-workers, as well as by other authors.
In order to obtain a specific expansion for the energy, it is

14
necessary to specify the expansions of the geminals. Silver haB
given the energy for the case where the geminals are eigenfunctions
2
of S and S as
z
E - I E(u) + E<v I(u,v) (11)
where
108
E(u) “ E C c E(yl,jjj)
ij Mi Mj
I(u,v) - E C 2 I(yi,vj)
i,j Mi vj
ECpi.pj) - + ^ |2 1 + 1 lh l ^ t21+1)i
+<*p,2i*ii,2j^P,2J+l*|i,2i+l) “ % t2i+l*y,2jl*p,2J+l
21+1 2j+l
I(yi,vj) - E E {(4 4 I* <j» )
m-21 n-2j U m ,im Vn
-(♦ 4 U ♦ ))
Mm vn Mm vn
(4- ,|h|4 ) - fix. 4 (l)h(l) 4 (1 )

Mi vj i Mi vj
( 4 4 |4 4 ) - //dT dT 4 C D 4 C D J l _ 4 <2 > 4 (2)

Mi vj Ur xl 1 2 Mi VJ ri2 un *1
These expressions may be further simplified once the spin of
each geminal has been specified. The energy expression may be put
in the form
E - 2 J £i hii + 2 <aij Jij + bij Kij> (12)
where
hu ' (tJhUi)
and
Kij " <+i*jUi*j>

where the coefficients f^, and b ^ are to be determined subject to
the orthogonality constraints.

109
Geminal Optimization
We wish to obtain the optimum geminal expansions such that we
minimize the total energy. To do this we need to optimize both the
occupation coefficients and the natural orbitals for each geminal.
It is important that we variationally determine the optimum geminal

18
natural orbitals and not guess them from other considerations.
The strongly orthogonal geminal wavefunctions are expected to yield
equivalent geminals which presumably should exhibit maximum locali
zation, and be recognizable as groups such as bonds, lone pairs or
inner pairs. 19 It is not satisfactory, however, i.e. it may lead
to erroneous conclusions, to use an alternate localization method
such as the Roothaan procedure to predetermine the natural orbitals;
we must optimize the partitioning of basis.
The optimization of the geminal expansion is formally a well
defined minimization problem. In practice, the minimization process
is rather complex and an iterative scheme is used. Alternately, we
optimize the occupation coefficients and the natural orbits until
self consistency is achieved.

110
Optimization of the Occupation coefficients
In order to obtain the optimum occupation coefficients for a fixed
set of natural orbitals, the expectation value of the energy is minimized
with respect to the occupation coefficients. This minimization is
subject to the normalization condition on the geminal.
We note that the energy expression for a strongly orthogonal
wave function may be written in the form
E(u) + E. I(u,v) + terms not Involving general A
■ cu + terms not involving general
The geminal energy eu may be defined as the expectation value of
an effective geminal hamiltonian.
ey - //dTjdtj A^(l,2) HMa,2)Aw(l,2)
where
H (1,2) - hl + h2 + ji- + k u / Z d l j d t ^ O . W
Variation of the energy with respect to the occupation coefficients,
subject to the normalization constraint, leads to a set of coupled
eigenvalue equations. For each geminal we have
(13)
For the ground state the geminal energies, are taken to be the lowest
eigenvalues of the matrices and the occupation coefficients as the

Ill
corresponding eigenvector of H^. Since the effective geminal operators
depend on the occupation coefficients of the other geminals, an iterative
process Is used. We guess an initial set of occupation numbers and
calculate an improved set for each geminal. This process is found
to converge very rapidly and is rather simple to Implement.

112
Optimization of the Natural Orbitals
The optimum natural orbitals are derived by minimizing the total
energy with respect to the natural orbitals which are subject to the
strong orthogonality and normalization constraints. This is a well
known problem in MC-SCF, multi-configuration self-consistent field
theory. The relationship to MC-SCF theory is easily seen by expand
ing the strongly orthogonal wavefunction in Slater determinants. We
have
(I)(J> (K)
*êpp H 2 2 2 1 ( 1 , 2 . . . .2 m )
3 i j p Ii.Jj___ Kk
(I)
where the summation, 2 implies the sum over the natural orbitals
i
belonging to the subspace of geminal I. The normalized and orthogonal
configuration functions, I. , . . are given by
1(1,2....2p) - A(2 "m/2) {[iK U M2) - M U M2))

Ii,Jj....Kk I2i 121+1 121+1 121
[M3) M 4 ) - M3) M 4 ) ] . . . [ M 2 m -1) M 2 m ) “ M2P-1) M 2 m ) H

J2j J2j+1 J2J+1 J2j K2k K2k+1 K2k+1 K2k
which may be expanded into a linear combination of Slater determinants.
The particular linear combination will depend on the spin states of
each of the geminals. For the case where the geminals are all singlet
coupled we have
1(1,2....2m ) - |x(D X(2) ....x (2m -1) x (2m > |

lijj Kk I2i 121+1 K2k K2k+1
- |MD M2)... , M 2 m - i ) 5(2 m )|

Ii Ii Kk Kk
113
^ may thus be put in the general MC-SCF form

” Ed $
SEP ill
where the coefficients, d_^ are not linearly independent as they are
in the geminal MC-SCF theory.
The energy expression for a normalized MC-SCF wavefunction is
E ■ J j W u ‘ ii + ii E1J(1Jikl)-8ii<1Jikl))
where
and the u)^^, ajj^ and are specific constants which depend on the
state of the wavefunction. The SEP energy, equation (12) is a
special case of this where we have

U
3
w ij
kl “ “ ij
O ij
Bkl " Bkl
We may thus use any of the MC-SCF formulisms for the determination of
the optimum natural orbitals. These procedures may not be the best
approach for the geminal optimization since they will not, in general,
take into account the simplified form of the energy expression.
Picturing the problem in this manner, however, allows us to use the
extensive research that is being done in MC-SCF theory. It emphasized
the difficulties in computing SEP wavefunctions and also may point
to ways of generalizing the SEP formalization.
Two main approaches can be distinguished in MC-SCF theory for

114
determining the optimum orbitals; either by forcing the equations for
the optimal orbitals into a pseudoeigenvalue form or by direct
minimization of the energy functional. Several reviews on the
pseudoeigenvalue approach have appeared recently both for the general

21
MC-SCF theory and for the restricted SEP energy functional. The
methods are based on forming the appropriate Fock operators. In
order to obtain a stationary point, the variation of the energy
should take into account the MO orthogonality. We thus need to
minimize the augmented functional
L - H - E X [<±(j»-«±J|]
lj iJ J
where are the Lagrange multipliers. The variation of L leads
to the Euler equation
^ |j> » £ X y |j> for all i
and
A
*lj “ Xji for all i,j
where the Fock operators, F^j, are defined by
Fu
and where and are the coulomb and exchange operators. We then
define a coupling operator R, constructed in such a manner that the
Euler equations can be reduced to a unique pseudoeigenvalue equation,
i.e. the off diagonal Lagrangian multipliers are eliminated.
R|i>»EjJi> for all i

115
This general approach was first proposed for SEP wavefunctions by

22 23
Kutzelnigg and in used extensively by Goddard and coworkers.
The energy minimization methods are characterized by a
parameterization of the orthogonal transformation mixing the orbitals.^
We initially start with a set of trial natural orbitals (Xy}. In
order to optimize the wavefunction we attempt to find a unitary
transformation T which produces a new set of orbitals {X^}.

M
X 1 » T X
M ■ JJ
such that the resulting energy Is stationary. The unitary transfor
mation matrix, T, of order n is characterized by n(n-l)/2 linearly
independent parameters. We wish to minimize the energy with
respect to the linearly independent parameters.

25
The simplest such procedure is the two by two rotation method.
For each pair of natural orbitals we form a new pair by the rotation
xj ■ cos 0 X^ + sin 0 Xj
Xj » cos GXj - sin 0 X^
The best value for the mixing parameter, 0, is that value for which
the energy is lowest. The method is straightforward to implement, and
convergence is guaranteed. It is, however, rather Inefficient; it is
necessary to transform some of the Integrals after each rotation. It
is also a difficult method to implement for large basis sets. Even
though the convergence for each rotation is quadratic, the overall
rate of convergence is linear, at best,

26
This method was generalized by Raffenetti and Rudenberg by
characterizing the order unitary transformation matrix with

I
116
n(n-l)/2 siraultanous rotations, the generalized Euler angles. This
approach seems Intractable In general, since it does not appear to
be possible to derive a simple procedure to minimize the energy
with respect to the Euler angles for an arbitrary n.
There are other parameterlzatlons of the unitary transformation
matrix available which lead to a more useful formulation. For

27
example, Yaffe and Goddard used
T - ea
28
where A is an antisymmetric matrix while Polezzo used Cayley's
formula
T - - I + 2 (I + X - X ) " 1
where X is a completely arbitrary (real) matrix. The general approach
is to expand the transformation matrix in terms of the independent
parameters. We truncate this expansion at a given order, usually
first order, and then minimize the energy with respect to these
parameters. Several minimization procedures have proved useful.

29
Saunders and Guest used this approach in computing SEP and
MC-SCF wavefunction; they defined a transformation matrix of the
form
T - I + X
where X is a skew-symmetric matrix, i.e. Xj^.
This is requiredfor the orthonormality of the transformed
orbitals to firstorder where <}>^ may be expressed sb
1 01
^ - E (6 jj + Xy) for i ■ 1 ,2 ,.. .m
117
The standard Newton Raphson procedure was used through which we
obtain a set of linear equations of order N(N-l)/2.

.2 .
(«Ji) x-o + k>lXjl (’V xik)
These equations are impractical to solve except for small cases since
».J '
the number of 2 derivatives is proportional to the fourth power of
the number of molecular orbitals. It is thus necessary to make some
simplifying assumptions in order to use this method. Saunders and
Guest neglected all of the off-diagonal second derivatives and used
a level shifting method to guarantee convergence, 30 that is
xji ' ■ “ (axjj x-o/ [U] X**0 + 0
where a, and 0 are parameters which may be chosen as deBired.
Unfortunately the quadratic properties of the Newton Raphson scheme
are lost.
Another method which has been shown to be similar to the Newton
Raphson scheme is the application of the generalized Brlllouin
theorem.
1X8
Generalized Brillouin Theorem
The generalized Brillouin Theorem for MC-SCF methods was intro-

31
duced by Levy; his derivation is summarized below.
The MC-SCF wavefunction can be written as a linear combination
of Slater determinants as
* " Edi A
lc
with the normalization condition
IdJ-l
k k
We need to calculate the variation of the total energy with respect
to the orbitals
6E - 2E dkd1 <6 *k |n|*1>

k,l
If is taken to be a Slater determinant
*k = |e1 (i)0 2 (2 ) - - 0 M (M)---.0 ij(M) |
where the 0^ are the spin orbitals, then we have
6 *. - E |fi1 (l)0«(2)** *60 (M) * • * 0 (p)|

K ME^ X L w V
We expand the differential elements 6 in terms of the set of
space orbitals
s* i " * x« +j
with the auxiliary conditions to preserve orthonormality to first order.
Xlj-Xjl (14)
1X9
Therefore, we have
6 *k «£ £ x.. ¥ <i-M)
iE*k j « k
where the 4»k(i+j) are constructed as follows: If the space orbital
occurs only once In 4>k then Is the determinant formed by
replacing by $j . If <J>^ occurs twice, that is with a and B spin,
then Is replaced by the sum of two determinants, the first
with and and the second with <|>j and In addition V^Ci**^) " 0
if does not contain orbital 4^.
Taking into account the orthogonality constraint, equation (14),
we have
6*k " I Xij
The variation of the energy may then be expressed as
6E - 21 X.,<i).(i-fj)|H|^>
i<j J
where
<Ki**j) - ^[^(i-Kj) - 4»k(j-vi)]

k
At the minimum energy we have 6E-0 which Implies that
<*(i*»j>|H|i|»> - 0
This relation is called the generalized Brillouin theorem and means
that the matrix elements of the Hamiltonian between the wavefunction 4/
and the linear combination of configurations 4>(i*-j) cancel out. It is
important to note that the generalized Brillouin theorem does not
say that single excitations do not contribute to the wavefunction, but
only that certain linear combinations cancel.

120
In terms of the transformed orbitals, we have to first order.
^ + 6i
J»
- if, + Z X,, ^(1-^j)

1<J 2
The determination of the optimum X ^ necessary to minimize the energy
may thus be treated as a super-CI wavefunction.
The relationship of this method to the Newton Raphson scheme is

32
apparent by noting that
(If,,)
\ ij xbo
I
-
The solution to the super-Cl eigenvalue problem amounts to solving the
set of linear equations
■ (»y * - o + L i ***■ ■ °
where
Gij,ki " 2 <H 1 +:)>lH l'Kk-*1)>
The second order derivatives used in the Newton Raphson scheme may be
expressed as
" 2«Ki^j)|H|^(H-j)> + 2<*|H|* >
The terms of the form <i|i|h |^( ’*‘^)> are much smaller than the other
k-*-l
terms and thus the two methods are closely related. The generalized
Brillouin theorem is preferred however since Cl methods are well
developed and large systems and basis sets can be treated.

121
Computation Method
The computation of the optimum SEP or MC-SCF wavefunction
proceeds as follows.
(1) The trial wavefunction Is expanded as a linear combination of
symmetry adapted configuration functions which may be expanded In
terms of Slater determinants.
* " EdA ±
1 1 1
(2) The coefficients d^ are determined by the standard variation
procedure for the MC-SCF method or by solving the coupled eigenvalue
equations for the occupation coefficients in the SEP formalism.
(3) The super-CI wavefunction Is set up
*sci - * * l <3 V ti*3)
and the linear coefficients are obtained by the variation method.
It Is important to note that the single excitation wavefunctions \Ji(l-*J)
are not normalized and are not in general orthogonal. Normalizing

33
the ^(i+j) results In slower convergence.
(A) The new set of orbitals Is formed according to the contraction
formula
♦i ■ *t+ j* V j
and is then orthonormallzed using either the Lowdin or the
Schmidt orthogonalization method. The basis set integralsare
then transformed to the basis set.
(5) The steps (2) to (4) are repeated until convergenceis reached,
i.e. until Xj_j" 0 for all i,j or equivalently until

122
<\|)|H|<Jj(i**j)> “ 0 for l<j
The configuration function, an<* single excitation

3#
functions iK^J) are constructed in terms of bonded functions.
The spin coupling for the bonded functions is described by a system
of parentheses coupling pairs of orbitals. A coupled pair of
orbitals (<{> ,<j>.) in the orbital product is associated with the

S u
spin factor
[a(l)B(2 ) - 0 (l)a(2 )]//2 " if s * t
and
[u(l)B(2)J if s - t
Any uncoupled orbitals are represented by an open parenthesis,
and are associated with an a spin factor. This results in
configuration functions with Ms - S, with 2S orbitals remaining
unpaired. For example, the bonded function
^ 1
corresponds to the following linear combination of Slater determinants
The single excitations are easily given in terms of bonded functions as
*K<i->m) - r r (♦14>n ) < * J * k > < * 1
» /T "
4i
K(i-*-l) *» / 2
123
The J 2 ~ factor is present since the single excitation functions are not
normalized.
The matrix elements over bonded functions are easily computed

35 We thus proceed by computing the super-CI
using standard methods.
hamiltonian matrix elements and solving the eigenvalue problem
(H - ES) X=0
where S is theoverlap matrix oftheconfigurations of t|/. The Lowdin
method was used totransform this into the standard eigenvalue

ui 36
problem
(H* - El) 0 0
where
H 1 » U+HU
and
X = UC
U - S"*
124
Application for SEP wavefunctions
Sample calculations on Be, Ne and CH^ have been performed to
show the applicability and usefullness of the generalized Brillouin
theorem for computing SEP wavefunctlons. Each geminal was required
to be symmetry adapted and singlet coupled so that the wave functions
meet the required symmetry conditions.

125
Beryllium
We have recomputed the SEP wavefunction of Be using the s and

37
s,p basis of Miller and Ruedenberg. The wave function for the
ground state Is written as
* - A {Ak (1,2)0k (1,2)Al (3,4)0l (3,4)}
where Av and A are spatial geminals of S symmetry describing the R

K. L
and L shells respectively and 0 and 0 are the singlet spin functions,
K L
0(1,2) - {a(l)B(2> - B(l)a(2)}/
The natural orbitals are constructed as a linear combination of real
Slater type orbitals and are required to have S symmetry. Each
natural orbital, Xuj , therefore is to be characterized by its 1, m

f*h
quantum numbers. Specifying the j n natural orbital therefore implies
an 1 quantum number and we designate the natural orbitals as X

Wjm
to distinguish the different m cases. The geminals, A^ and A^ are
taken to be of the form i

A (1,2) o EC {(21+1)
V j UJ
The starting natural orbitals were taken to be the Schmidt orthogonallzed
Slater type orbitals. The single excitation functions, ^(l^J) were
constructed for all natural orbitals with the same 1, m. Since the
set of orbitals for fixed u and j are required to be equivalent,
we have
■Kl+l1) - S (<K (lm+l1!!!) - (l^n+lm)}

m=-l K K
126
The same results are obtained with considerable computational savings
by using only one of the ra values In forming the single excitations, i.e.
iKl^l1) “ ^.(lTTH-l^m) - i|i (l*nr*-lm) for -l<m<l

K iv
The convergence of the generalized Brillouin theorem method was
good even when the Initial choice of orbitals was poor. If the
starting orbitals were poor then the energy obtained on successive
iterations would oscillate for the first few iterations and then
converge montonically. For partially converged orbitals we find that
E(n+D < E(n) < E(n)

sex
where E(n^ is the energy for the nttl iteration and E^g^ is the energy
of the single excitation Cl. The number of iterations necessary
for convergence varies with the quality of the initial orbitals, the
convergence criteria, and the rank of the single excitation expansion.
In general, we found that the energy converges very rapidly but that
several additional iterations are necessary for the orbitals to

2 -7
converge. The convergence criteria we used was that E <, 10 .
This corresponds to an energy which converged to approximately 8
digits. At convergence the matrix elements (iji|h |iKl-*-j)) were
typically on the order of 10“^. If approximate HF orbitals are used
for the starting orbitals the above convergence was met in approximately
10 Iterations.
127
TABLE I
Be -
OrbitalB (Exponents)
K shell IS 3.1*05
2S 1|.292
2P 5. U85
L shell 2S .993
2P ,978 rank of single excitation CI®1*
Iteration Energy
JSCI
1 -13.5201*5667 -ll*.0 1 9 5 6 0 7 I* .101*3379
2 -ll*.614691*9051* -ll*.61*759311*3 ,00031*66

3 -ll*.61*76981+1* -ll*.61*769861*04 .0000001
1* -ll*.61*77001*7 •ll*.61*77001*7
-ll*.6 1 * 7 7 0 0 5
Cl Energy -ll*.61*809671
Orbitals
(Exponents)
IS 3.405
2S 4,292
3S 5.068
2P 5.485
3P 6.27
2S .993
2P .978
Rank of single excitation Cl « 9
Iteration E
ESCI ZijXij
1 -12.3970165 -13.13286813 .2507099
2 -14.47864102 -14.62439289 .0033809
3 -14.651906304 -14.65206662 .000155313
4 -14.652160535 -14.652160599 .0000001
5 -14.652161482 -14.652161482
6 -14.65216153
Cl Energy -14.65255612
129
Orbitals
(Exponents)
IS 2 ,9 1 4 2 2
IS 5.3*4075
2S .99660
2S 2.69580
IS 1,2
23 *4.7
2S 1,2
3S 1.2
rank Geminal 1 3
Geminal 2 3
rank of single excitation Cl 0 28
iteration E
ESCI EiJXU
1 .278696 -13.016881 1610.706

2 -11.09*47778 -13.3590919 1185. *421
3 -13.147501425 -1 I4.112366 63614.368
U -13.085678 -1*4.3*4638*4 19.63275
5 -114.1461456*4 -1 I4.578029 6.014807
6 -H 4.I4 2 6 5 6 9 I -1*4.5809*433 22.63*456
7 -114.581539986 -1 *4 . 5 8 7 1 5 7 6 9 5.996523
8 -1*4.58512915 -1 *4 . 5 8 7 7 6 1 3 3 .7313887
9 -II4.5 8 8 OI4I4OI4 -II4.5882967 .3039059
10 -1*4.58033*4575 -1*4.588*42002 .05616239
15 -1*4.58839829*4 -1*4,5885011*49 ,000022*4
130
Neon
Neon was a very difficult case to treat with the generalized Brillouin
theorem approach since we were requiring each geminal to be of S symmetry*
The difficulty is due to the requirement that the wavefunction can not in
clude the HF configuration as well as to the fact that the single excita
tion configurations ^(i+j) generally had a lower energy than 'f'ggp. Two
approaches were used to force convergence. The first method used waB first
order Rayleigh-Schrodinger theory,
-<ifr tt|^(i-> .l)>

Xij “ - <tp(i^)[HU(i-vj)>
Convergence however was found to be slow especially if several orbitals were
mixed simultaneously. The second approach used was a root shifting method,
We added a diagonal matrix to the hamiltionian matrix. The constant, A is
arbitrary and was choBen such that EgEp was lower than the other diagonal
elements. If the value of A is too small the single excitation terms will
dominate the expansion and the calculation may not converge. If A is too
large, however, the convergence will be very slow. The overall rate of
convergence is approximately first order.
The results of the canputation are poor. This is not unexpected since
we are not including the Hartree Fock configuration.

131
TABLE II
tie EHp = -128.54705
basis 1
IS 9.48486 4 - configuration functions
IS' 15.56590
2S 2.86423 E = -115.3824
2S' 4.82530
2P 1.45208
EijXij “ 1,79 X 10
2P' 2.38168
2P" 4.48489
basis 2
basis 1 + 3P 1.45208
3P1 2.38168
3P" 4.48489
4 - configuration functions 108 Slater determinants
E » -121.76846
EijXij " 6,18 x 10~5
132
Methane
The SEP wavefunction for methane using a minimal and double zeta
Slater basis have been computed. The geminal natural orbitals were con
strained to be symmetry orbitals. The basis sets, the geometry and the
symmetry orbitals are given in table III,

133
TABLE III
minimal basis set
orbital exponent
1SC 5.78
23 „ 1.76
2P. 1.76
IS, 1.17
H
Double zeta basis
orbital exponent
M C 5.2309
“ c 7.96897
2SC 1.16782
2S£ 1.82031
2PC 1.25572
2P £ 2.72625
1.1*
“ K 1.625
geometry coordinates 1* ** 2 . 0 5 a.u,

un
0 . 0 . 0 .
Hi q q *
K2 -q -q q
h3 q -a -a
\ -q q a
Symmetry Orbitals
135
The application of the generalized Brillouin theorem thus provides
a straightforward and efficient procedure for the computation of separ
ated electron pair wavefunctions. The method is eaBy to implement and
we are able to utilize existing Cl software with only slight modifications.
In addition, if we use a formula type Cl approach, we may take advantage
of relationships among the occupation coefficients} thus utilizing the
simplified form of the energy functional.
It is alBo interesting to note that the orbital optimization using
the generalized Brillouin theorem does not require the strong orthogonal
ity constraint. We may therefore determine the optimum orbitals for a
general APG wavefunction using the same procedure. The generalized Bril
louin theorem is a general method and is applicable to any MC-SCF wave
function, To compute the general APG wavefunction, we thus only need a
procedure for computing the occupation coefficients.

136
Determination of Occupation Numbers for an APG Wavefunction
The APG wavefunction is of the form
* " °SL a |I \ C2^ 1*2^
where we require that each geminal be normalized
/Aij(l,2)Ap(l,2)dT1dT2 - 1
The geminals are not required to be spin or symmetry adapted since the
A
projection operator 0g^ will project out the desired Btate. In general,
therefore, we may express each geminal as a linear combination of a sing
let and a triplet component
A^(l,2) - Aj(l,2) + a J(1,2)
For wavefunctionB of the APG form, however, the NSO's of the gem
inals are not the NSO's of the total wavefunction t|/i in general p is not
normalized. Every geminal will be of the form
A (1,2) - EC .♦ .
IT 1 ± pi yi
with
2
ec : - i
i pi
where is a 2 by 2 Slater determinant or possibly a linear
combination of 2 by 2 Slater determinants, We may always simplify
the wavefunction expansion by choosing the orbital basis to be the

137
NSO's of at least one geminal.
We can now proceed as before by expanding $ in terms of
configuration functions
® £dv^K
tfi
where K
d, -,n C .
k (pj) pj
with (pj) representing the occupation coefficient connected with $ .
K
Each coefficient d contains one and only one occupation coefficient
K
from each geminal. The wavefunction, may thus be written as
^ J Cpi % i £or a11 p

where
(pi)/(Pi) \
♦ > - e n cT
vi K Upi V
x (pi)
where the summation £ implies the sum over all configuration
K
containing i^1 terms of geminals p .
The energy expansions may thus be put in the form
/(p)(p> u W / M M
E E C ,C E E C C .S..
I f j Pi Pj iji/l ± j Pi pj ij
where
*)
Hij -V ' V
and
S.J - <* I# )
ij Pi' Pj
To determine the optimum coefficients, we require that G
be stationary with respect to variations in the This results
in the pseudoeigenvalue problem
(Hp - ES)CP - 0
As in the SEP case, we can solve these equations for each geminal
and iterate until converged.

139
Singlet Triplet Pairs
The wavefunction Is taken to be of the APG form
* ■ °SL ■ ‘‘jya'-i-.ao
where the geminals are strongly orthogonal and are linear combinations
18
of a singlet and a triplet component.
\ (1*2) - aJ1)(1,2) + aJ3)(1,2)

The singlet term, A^^ has the form given by equation (8) and the
(3)
triplet term, A^ is taken to be a linear combination of the three
triplet couplings. The wavefunction, i|> is required to have a
specified spin and spatial symmetry. If the geminals are normalized,
the wavefunction will not be normalized.
Consider the case of the singlet S state of Be with each
geminal having rank 3.
A],(1,2) - Cn <t»1<}.101(l,2) + C124>24*201<1,2> + C13(<(.1<(»2- ^ 1)03(1,2)
A3 (l,2) - C21*3^3ei(l,2) +
where 0^, 6^ are the corresponding singlet and triplet spin functions.
The geminal normalization conditions are,
C11 + C12 + C13 - 1
C21 + C22 + C23 * 1

The spin projected wavefunction 1b therefore of the form.
^ “ ^SEP + C13C23
nr <<+l+3)(* 2 V + <*1* 4 > ( V 3 )>
140
where ^SEP
iJ'gjjp corresponds to an unnormalized separated electron pair wavefunction.
The effect of considering each geminal as a singlet triplet pair is
that of introducing some lntergemlnal correlation by including some
two electron transfer configurations.
The results of a rank 3 and 6 singlet triplet pair calculation are
given in Table IV. The natural orbital optimization is no more
difficult than in the separated electron pair case. Since the single
excitation functions involve considerably longer expansions, the
computation time per iteration was longer. The wavefunction
converges in about 5 iterations if the separated electron pair
natural orbitals are taken as the initial orbitals. No convergence
difficulties were encountered In the occupation coefficient
optimization.
Table IV
Be - singlet triplet pairs
I ' - geminals of rank 3
E - -14.58776165 ESEP " “14‘58776098
Occupation Coefficients
* ^SEP
.9997228 .9997230
'11
-.235457(-1) -.2353444(-1)
'12
-.1679033(-3)
'13
-.9990612 .9990523
'21
.4332169(-1) -.4352496C-1)
'22
-.1680396(-3)
'23
II Geminals of rank 6.
AjU.2) - C + C12(*2*2) + C13^3*3> + C14[V
+ o15Uv ^ 3 + c16C*2.*3]e3
when [<frr $2] - (♦1(1)*2(2) - ^ (1)^(2))

E = -14.5885419 ESEP “ “W *5883948
Occupation numbers
* ^SEP
.9996825 .996762
C11
-.2501696C-1) 2526567(-1)
C12
-.2998274(-2) -.3028769(-2)
C13
-.5190447(-4)
Cl*
-.1406607(-4)
C15
-.2500229(-5)
C16
+.9995322 .9997017
C21
-.3495385(-2) -.3352696(-2)
C22
-,3038393(-l) 2419287(-1)
°23
roo
.127550M-3)
•*»
-.1870842C-3)
C25
-.5251817(-5)
C26
143
Interacting Geminal Model
The Interacting geminal model was introduced by Silver as a
means of weakening the strong orthogonality constraint while still
keeping the formalism t r a c t a b l e I n this model each geminal has a
natural orbital expansion in terms of all of thenatural orbitals
of the system. For the case of singlet coupled geminals we have
Ap - (I Cv i Xi(l)X1(2))01(l,2)
where the X^ are the natural orbitals of thesystem.* The geminals are
constrained to be normalized, I.e.
We have performed a small Interacting geminal type calculation on
Be using a small s orbital basis. We have, however, limited the
natural orbital expansion range and required that the configuration
functions be orthogonal. These are arbitrary constraints restricting
the form of the wavefunction but what are believed to be the more
important configurations have been included in the wavefunction. These
constraints are not necessary for either the occupation number or
natural orbital optimization; they are imposed for convenience.
For example, consider the geminal expansion obtained by including
the PNO's of the SEP wavefunction in the natural orbital expansion of
the other geminals. For Be we have
* It is useful to note that if two or more geminals have the same set
of occupation coefficients, {C .}, the geminals are called Identical
geminals. The case where all trie geminals are constrained to be the
same is referred to as the identical geminal or biorbital model.
Requiring the configuration functions to be orthogonal excludes the
configuration C _,C_,( CA^<b_) from the wavefunction since this

14 24 4 4 1 1
term is not orthogonal to the PNO configuration function. Since
the coefficients and C ^ are expected to be small compared to
the PNO coefficients we assume that the effect of neglecting this
term will be small.
.We have computed the optimum geminal wavefunction for Be using
this model. That is we have determined the optimum geminals of the
form given above for the wavefunction
*2 ■ *1 + °13 C24 C*l*l>«3+3) + C14 C23 < W (W
where
*1 ■ ’''SEP + C12 C24 (*i*i)(*2*2> + C14 C22 <+4*4> W 5*5)
In addition as a further check on the convergence of the method and
a test of the validity of the model we have computed the optimum
geminals of ^ . The results are expected to be similar as the
configurations with the largest coefficients are included in The
results are summarized in Table V.

Table V
Interacting geminalB
ESEP - -14.58839484
lj
±<i
-14.588587379 « 2 x 10"7
-14.588587775 - 1 x 10“6
Occupation coefficients
O',SEP ♦l *2
.9997017 .9997012 .9997001

11
'12
-.3352696(-2) -.2425587(-l) -.2430008(-1)
'13 -. 241928 (-1) -.2939156C-2) -.2942565(-2)
14 .7783324(-3) .7636726(-3)
.9996762 .9991309 .9991559

'21
'22
-.2526567(-1) ■.4150040 (-1) -.04089408
-.3028769(-2) -.3739843(-2) -.3739606(-2)

'23
-.1123953 (-2) .1108543(-2)
24
Uf>
Conclusions
The generalized Brillouin theorem provides an effective procedure
for the computation of SEP and APG wavefunctions. Using this technique
it is possible to explore the utility and validity of a variety of APG
models. The difficulty and computational effort in determining the
APG wavefunction has been shown to be similar to that for determining
a similar MC-SCF wavefunction. The difficulty increases with the size
of the configuration function space and the size of the set of basis
functions. Starting with HF-SCF or SEP orbitals the convergence
appears to be excellent.
147
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VITA
Harry Partridge III
Place and Date of Birth
Newport, R.I. June 25, 1950
Education
Bayslde High School Virginia Beach, Virginia 1968
Virginia Military Institute Lexington, Virginia 1972

B.S. Chemistry and
Mathematics
Indiana University Bloomington, Indiana 1978

The Geminal Model and The Fourier Transform Method For The Evaluation of Multicenter Slater Integrals

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The Geminal Model and The Fourier Transform Method For The Evaluation of Multicenter Slater Integrals

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IN FO R M A TIO N TO USERS

The following explanation of techniques is provided to help you understand

2. When an image on the film is obliterated with a round black mark it is an

4. For any illustrations that cannot be reproduced satisfactorily by

FOR THE EVALUATION OF MULTICENTER SLATER INTEGRALS

Harry Partridge III

Partially supported by grants from the

National Science Foundation

Principal Investigator: Harrison Shull

Submitted to the Faculty of the Graduate School in partial

fulfillment of the requirements for the degree of Doctor of

Philosophy in the Department of Chemistry, Indiana University.

This is to certify that the thesis submitted by Harry Partridge III

The author would like to express his gratitude to Professor

Harrison Shull and Professor Stanley Hagstrom for their guidance

and support throughout the course of this work.

The author Is Indebted to Dr. James Sims for his assistance

the Quantum Chemistry Group at Indiana University, Dr. James

The author is also grateful to his parents, Helen and Harry

Partridge, to Penny Posthumus-Meyjes, and to Irene Waight for

their invaluable assistance in the preparation of this manuscript.

EVALUATION OF MULTICENTER SLATER INTEGRALS

The energy expectation value of a system is given by

function, If V is approximated with a linear combination of antisymme­

trized products of one electron functions, then the energy expression

for atomic and molecular systems reduces to a linear combination of one

tions, The evaluation of these integrals is an essential step in any

The orbital bases used in ab Initio calculations today are

principally of two types: Slater or exponential and gausslan type

normalized spherical harmonics. Both of these basis sets are complete

in the limit of an infinite expansion^" and the choice of a one electron

basis is in many ways a matter of convenience. Slater orbitals offer a

in a central attractive coulomb field can be written as a finite linear

combination of Slater type orbitals or an infinite expansion of gaussians.

b. A Slater basis satisfies the cusp condition at r ** 0 and has the

It is thus not surprising that fewer Slater type orbitals than

gaussian type orbitals are required to achieve a given accuracy of approx-

to describe electron distributions in many electron systems.

In spite of the obvious advantages of Slater type orbitals, most ab

initio calculations on polyatomic molecules have used a gaussian type

basis. This is due essentially to the ease in computing multiccnter in­

tegrals over a gaussian basis and the difficulty in obtaining accurate

Individual multiccnter Integrals over gaussians may be on the order of

over Slater type orbitals.

For many calculations, a gaussian basis set is clearly the more

efficient, even considering that a larger one electron basis is needed.

If one is attempting to obtain highly accurate results then the advantage

integral computation time becomes less of a stumbling block. The

In addition, since the number of integrals increases as N**, where N is

large scale MC-SCF and Cl calculations become excessive. A Slater

orbital basis, giving a more compact expansion, is thus often desir­

able, and more efficient.

The difficulty in using a Slater basis, however, is the general

unavailability of computer routines to compute accurate multicentcr

integrals over Slater orbitals, particularly over higher angular

cluding these polarization orbitals,^ and indicate that the principal

In this work we are concerned with the Fourier transform

method, its implementation and use for the computation of multicenter

Multicenter Electron Repulsion Integrals

We are primarily Interested in the evaluation of the multi­

center two electron integral

where (r) is the charge distribution arising from the product of

orbitals located on centers a and b. Wien a gaussian orbital basis is

function, If V is approximated with a linear combination of antisymme

basis. This is due essentially to the ease in computing multiccnter in

orbital basis, giving a more compact expansion, is thus often desir

We are primarily Interested in the evaluation of the multi

Numerous studies on the evaluation of multicenter Slater inte

The transform methods have recently received considerable atten

formally equivalent to the Fourier transform method. Their routines com

1 ' < ° 3 I ru " ‘ I ♦?>