Framework for calculation of Breit-Pauli Spin-Orbit 1

Hamiltonian using Auxiliary Density Fuctional Theory 2

Otto Hahn Herrera, Emilio Orgaz, Andreas K oster, Bernardo Z u niga Guti errez 3
June 6, 2013 4
Abstract 5
A method for the determination of spin orbit coupling using an effective nuclear charge 6
one-electron Breit-Pauli Hamiltonian is developed for use in auxiliary density functional 7
theory(ADFT). Using a single Slater determinant wavefunction formalism, the method relies on 8
the methodology of Mc Weeny for the resolution of the spin integral using transition density 9
matrices and the corresponding orbitals of L owdin for the biorthogonalization of the 10
wavefunctions. The calculation of spin orbit coupling constants for diatomic hydrides was used 11
as calibration and comparison with other methods is shown. 12
1 Introduction 13
Non- adiabatic reactions occur when a transition from one Potential energy surface (PES) to another 14
appear along the reaction coordinate. This reactions cannot be modelled using the traditional Born- 15
Oppenheimer approximation. The interaction between the two PES is given by the spin-orbit cou- 16
pling hamiltonian. Spin orbit coupling through the use of the Breit-Pauli spin-orbit hamiltonian is the 17
mechanism responsible for the coupling of the different PES. Ab initio molecular orbital and Den- 18
sity Functional Theory (DFT) methods are successful in ground state systems,in recent times, more 19
interest is been given to radiantionless transitions which depend heavily on their description in spin- 20
orbit (SO) coupling.The pioneering works of Furlani and King [furlani] and Matsunaga, Koseki and 21
Gordon [matsunaga1] using MRCI wavefunctions and one- and two-electron Breit Pauli operators are 22
currently used to calculate magnetic and photochemical properties and reactions. But although for- 23
mally correct approximations are difcult to use in large molecules because of the multideterminantal 24
1
approximation used in the wavefunction. To reduce the computational lload, Bearpark [bearpark] 25
developed a one determinant wavefunction approximation and used it successfully to describe the 26
spin orbit coupling of selected systems. Following along this line Chiodo and Russo [chiodo] using 27
a Breit-Pauli formalism use effective nuclear charges to approximate the one- and two-electron spin- 28
orbit hamiltonian using only a one-electron formalism in density functional theory. the following work 29
presents the theoretical framework developed thus far, and the results of the calibration comparing it 30
to the data available in the previously cited works. 31
2 Methodology 32
Let
M
and
N
be single Slater determinants

M
= C
1
_

M
1
(1) . . .
M
n
_
(1)

N
= C
2
_

N
1
(1) . . .
N
n
_
(2)
Where C
1
and C
2
are the normalization constants and the functions are orthogonal within the
determinants. The nonorthogonality between the different sets is represented by the overlap matrix S
S =

M
|
N
_
(3)
This matrix is generally not Hermitian. 33
We biorthogonalize both sets by means of unitary transformations that leave
M
and
N
invariant 34
except in a phase factor. 35

M
=

M
V (4)

N
=

N
U (5)
2

M
=
M
|V
T
| = C
1
|V
T
|
_

M
1
(1) . . .
M
n
_
(6)

N
=
N
|U
T
| = C
1
|U
T
|
_

N
1
(1) . . .
N
n
_
(7)
This transforms the overlap matrix as: 36
S

M
|
N
_
= U
T
SV (8)
We now have to produce the desired matrices U and V First we dene a matrix Q that is hermitian
as:
Q = S
T
S (9)
And we let V be formed by the orthonormal eigenvectors of Q. 37
QV = V (10)
Where is a diagonal matrix made from the eigenvalues of Q. 38
Premultiplication by V
T
yields 39
V
T
QV = V
T
V (11)
V
T
S
T
SV = I
(SV)
T
SV = (12)
3
Since is diagonal, this implies that the columns of SV are orthogonal to one another. Moreover
the eigenvalues
ii
are nonnegative since they are the square of the norms of these columns. If the
ii
are also nonzero we can construct the diagonal matrix
1/2
and the unitary matrix U
U = SV
1/2
(13)
it then follows that 40
S

= U
T
SV (14)
=
1/2
V
T
S
T
SV (15)
=
1/2
(SV)
T
SV (16)
=
1/2
(17)
=
1/2
(18)
which has the requiered diagonal form. 41
In the formation of
1/2
we choose the positive square roots. 42
The actual number of nonzero eigenvalues is equal to the rank r of S
T
S. When this is less than the
dimensionality n it becomes impossible to construct U so we need to revise the argument slightly. Let
the rst r columns of U be constructed as before:
u
i
=
1/2
ii
Sv
i
i r (19)
and from 12
Sv
i
= 0 i > r (20)
so that 18 is satisied if the last n r columns of U are formed as an orthogonal complement of 43
the rst r columns. Thus a corresponding orbital transformation is possible under all circumstances. 44
The one-electron spin-orbit coupling operator in atomic units has the form: Where N
C
denotes 45
the number of nuclei and c denotes the speed of light in atomic units. Before we apply this operator 46
4
we rst recall the action of the spin vector operator (

S =

S
x

i +

S
y

j +

S
z

k) on molecular spin-orbitals: 47

S
x

j
=
1
2

j
,

S
y

j
=
i
2

j
,

S
z

j
=
1
2

j
, (21)

S
x

j
=
1
2

j
,

S
x

j
=
i
2

j
,

S
x

j
=
1
2

j
. (22)
Now the spin-orbit coupling (SOC) matrix elements are calculated as the expectation value be-
tween two different electronic states of the same system:

M
|

H
SO
|
N
. (23)
with 48

H
SO
=
n

j=1

h
SO
(j) (24)
Where n denotes the number of electrons in the system. In this case both electronic states are
expressed by single Kohn-Sham determinants. They always differ by one spin ip according to the
SOC selection rule and are always the high spin conguration of their corresponding multiplicity. In
other words, the unpaired electrons will always occupy molecular orbitals. Thus the rst electronic
state, tagged from now on with the superscript M, has the monodeterminantal expression,

M
(r) =
1

n!
det |
M
1
(r
1
)
M
2
(r
2
) . . .
M
p
(r
n
)|, (25)
while the second electronic state, tagged with the superscript N, has the expression: 49

N
(r) =
1

n!
det |
N
1
(r
1
)
N
2
(r
2
) . . .
N
q
(r
n
)| (26)
The wavefunctions have to be also eigenfunctions of the spin operator [chiodo, bearpark] 50

M
=

M
(r), S
M
, M
M
s
_
(27)
5

N
=

N
(r), S
N
, M
N
s
_
(28)
Applying the spin-orbit operator to the trial wavefunctions: 51

M
(r), S
M
, M
M
s

1
2c
2
N
C

C=1
Z
eff
C

N
(r), S
N
, M
N
s
_
(29)
this equation can be rearranged as:
1
2c
2
N
C

C=1
Z
eff
C

M
(r), S
M
, M
M
s

N
(r), S
N
, M
N
s
_
(30)
To integrate over spin st a coordinate transformation of the spin operator from cartesian coordi- 52
nates to spherical is made: 53
S
1
(i) =
1

2
[S
x
(i) +iS
y
(i)] (31)
S
1
(i) =
1

2
[S
x
(i) iS
y
(i)] (32)
S
1
(i) = S
z
(i) (33)
Now the expressions of the cartesian coordinates are rearranged in terms of the spherical ones: 54
S
x
(i) =
1

2
[S
1
(i) iS
1
(i)] (34)
S
y
(i) =
i

2
[S
1
(i) iS
1
(i)] (35)
S
z
(i) = S
0
(i) (36)
6
The transformation constants are dened as: 55
C
x,1
=
1

2
(37)
C
x,1
=
1

2
(38)
C
x,0
= 0 (39)
C
y,1
=
1

2
(40)
C
y,1
=
i

2
(41)
C
y,0
= 0 (42)
C
z,1
=
1

2
(43)
C
z,1
=
1

2
(44)
C
z,0
= 1 (45)
Now, using the transition spin rules and the Wigner-Eckart theorem: 56

M
(r)S
M
, M
M
s
|S

(i)|
N
(r)S
N
, M
N
s
= (1)
S
M
M
M
s
C
,M
M
s
M
N
s
G(S
M
, M
M
s
, 1, (M
M
s
M
N
s
), S
N
, M
N
s
)
_

(r), S
M
|

S

|
N

(r), S
N
_
(46)
Following McWeeny [mcweeny] the integration over spin 57
_

(r), S
M
|

S
z
|
N

(r), S
N
_
=
(1)
S
M
M
M
s
C
,M
M
s
M
N
s
G(S
M
, M
M
s
, 1, (M
M
s
M
N
s
), S
N
, M
N
s
)
1
2
_

(r)|
N

(r)
_

(r)|
N

(r)
_
(47)
Finally to this expression is applied the angular momentum operator: 58
7

H
SO
_
= (1)
S
M
M
M
s
C
,M
M
s
M
N
s
G(S
M
, M
M
s
, 1, (M
M
s
M
N
s
), S
N
, M
N
s
)
1
2
__

(r)|

L|
N

(r)
_

(r)|

L|
N

(r)
__
(48)
As the top congurations have an excess of density resulting in:

H
SO
_
= (1)
S
M
M
M
s
C
,M
M
s
M
N
s
G(S
M
, M
M
s
, 1, (M
M
s
M
N
s
), S
N
, M
N
s
)
1
2
__

(r)|

L|
N

(r)
__
(49)
In the case of an orbital discoincidence and represent the same spin state, for example , then 59
it foolows that: 60
_

h
SO
(n)
_
=
1
2n
_

M
j

N
C

C=1
Z
eff
C

p
z
(

C)

N
k
_
n

m,n=k,j
_

M
m

N
n
_
(50)
A spin discoincidence means and spin states are not equal. Analizing the state where denotes 61
state while denotes state. 62
_

h
SO
(n)
_
=
1
2n
_

M
j

N
C

C=1
Z
eff
C

p
x
(

C)

N
k
_
n

m,n=k,j
_

M
m

N
n
_ n

m,n=k,j
_

M
m

N
n
_
+
i
2n
_

M
j

N
C

C=1
Z
eff
C

p
y
(

C)

N
k
_
n

m,n=k,j
_

M
m

N
n
_
(51)
This expressions can be further simplyed by noting the overlap of the modied states:
n

j=1
_

M
(mj)

N
(nj)
_
= S
ij
(52)
Is a singular value of S. Then for the modied overlap matrix: 63
S

ij
= d
i
d
i
| = S
ij

ij
=
1/2
(53)
8
Multiplication by the inverse of in both sides: 64
_

M
|

H
SO
|
N
_

1/2
=

H
SO
_
S

1/2
(54)
_

M
|

H
SO
|
N
_

1/2
=

H
SO
_

1/2

1/2
(55)
_

M
|

H
SO
|
N
_

1/2
=

H
SO
_
E (56)
_

M
|

H
SO
|
N
_

1/2
=

H
SO
_
(57)
Simplifying the equations to (in the general case):
_

h
SO
_
=
1
n
_

M
j

h
SO

N
k
_
(58)
And for the orbital discoincidence: 65
_

h
SO
(n)
_
=
1
2n
_

M
j

N
C

C=1
Z
eff
C

p
z
(

C)

N
k
_
(59)
and the spin discoincidence: 66
_

h
SO
(n)
_
=
1
2n
_

M
j

N
C

C=1
Z
eff
C

p
x
(

C)

N
k
_
+
i
2n
_

M
j

N
C

C=1
Z
eff
C

p
y
(

C)

N
k
_
(60)
2.1 The equations in matrix form 67
For the implementation of the method is easier to work this equations in matrix form. It shall express 68
the wavefunctions in terms of density matrices formed by the coefceint matrices C
M
and C
N
69
From this matrices the overlap matrix S
MN
is generated 70
9
S
MN
= C
MT
C
N
(61)
S
MN
is not a square matrix. So matrix Q is generated as: 71
Q = S
MNT
S
MN
(62)
diagonalization of Q to obtain its eigenvalues and eigenvetors V 72
QV = V (63)
Fromn the identity in L owdins method matrix U is formed as 73
U = SV
1/2
(64)
And calculate the orthogonal coefcients D
M
y D
N
as: 74
D
M
= C
M
U (65)
D
N
= C
N
V (66)
With the pairwise orthogonal matrices calculation of the transition spin density matrices for each
spin P
MN

and P
MN

:
P
MN

= D
MT

D
N

(67)
P
MN

= D
MT

D
N

(68)
And calculate the spin density matrix as the excess spin 75
10
Q
s
=
1
2
_
P
MN

P
MN

_
(69)
To integrate over spin multiplication by the corresponding transformation coefcient c
i
and the 76
transition Clebsch-Gordan coefcient 77
S
i
= c
i
jm
jn
Q
s
(70)
To this matrix applying the angular momentum operator and multiplication by the effective nuclear 78
charge Z
eff
C
79
H
SO
=
1
2
Z
eff
C

p
i
S
i
(71)
3 Results and Analysis 80
For the calibration of the method the diatomic hydrides AH were calculated using the functional PBE 81
of Perdew, Burke and Erzenhof [pbe] and the base TZVP of Dunning [tzvp] in the framework of 82
ADFT. In the case of single atoms we implemented a routine to give the ne structure splittings using 83
the Russell-Saunders formulation: 84

H
SO
=
1
2m
e
c
2
1
r
V
r

L

S =

S (72)
Note that the

L

S product can be written in terms of

J
2
,

L
2
and

S
2
as follows,

L

S =
1
2
(

J
2
85

L
2

S
2
), because,

J
2
=

J

J = (

L +

S)(

L +

S) =

L
2
+

S
2
+ 2

L

S, and, since the unperturbed 86
wave function is an eigenfunction of

L
2
,

S
2
and

J
2
, 87

L

S| >=
1
2

2
(

J(

J + 1)

L(

L + 1)

S(

S + 1))| > . 88
Therefore, 89
E
SO

1
2

2
< >
_

J(

J + 1)

L(

L + 1)

S(

S + 1)
_
. 90
11
Estado E
exp
E
calc
error % error
3
P
1
16.42 16.43 0.01 0.06
3
P
2
43.42 32.86 10.56 24
Table 1: Splittings of the
3
P states of atomic carbon calculated using Russell-Saunders splitting Re-
sults are compared to the spectroscopical tables of Moore [moore]. Effective nuclear charge was
calculated to match the experimental splitting.
It is important to note that, due to the spin-orbit coupling, the total energy of a state depends on 91
the value of the total angular momentum quantum number

J. Furthermore, each of the energy levels 92
is (2J+1) times degenerate, as determined by the possible values of M
J
. For example, when L=1, and 93
S=1/2, then the possible values of J are 1/2 and 3/2, since (J=L+S, L+S-1, ..., L-S). The expression for 94
the potential and the
1
r
parameter were taken from the hydrogenoid atom. 95
The results for the single atom calibration are the 3P states of the carbon atom. and 1 96
3.1 Diatomic Hydrides 97
The determination of the spin-orbit spitting constant for the diatomic hydrides was carried on the 98
ADFT framework using the PBE functional [pbe] with rthe PVTZ [tzvp] base as implemented in the 99
deMon2k suite. For comparison we searched the literature and compare to values calculated using 100
MRCI by Matsunaga and Koseki [matsunaga1], Hartree-Fock as implemented by Bearpark [bearpark] 101
and DFT [chiodo] The effective nuclear charges were the same as those reported by Russo [chiodo]. 102
Molecules were aligned on the z axis, and the z component of the spin-orbit operator is responsible 103
for the coupling between states
x
y
y
. In table 2 we indicate the molecule, the calculated states are 104
the same as those reported elsewhere [matsunaga1, furlani, chiodo]. 105
4 Conclusion 106
In this paper a method for calculating spin-orbit energies within the ADFT framework is developed. 107
Our results show that this method is adequate for problems where multiconguration problems are not 108
involved. Our results over the 3

and 2

congurations are in good agreement with the available MC 109

12
molecule E
exp
E
MCSCF
(%) E
DFT
(%) E
ADFT
(%)
AlH 40.20 39.43 (1.92 ) 42.64 (-6.07 ) 38.56 (4.08 )
AlH
+
108.00 93.33 (13.58 ) 113.67 (-5.25 ) (100.00 )
AsH -615.40 -629.82 (-2.34 ) (100.00 )
BH 5.95 5.97 (-0.34 ) 4.51 (24.20 ) 5.49 (7.73 )
BH
+
14.00 15.02 (-7.29 ) 14.47 (-3.36 ) (100.00 )
BrH 1184.90 1184.90 (0.00 ) (100.00 )
BrH
+
-2652.80 -2493.98(5.99 ) -2888.60(-8.89 ) -2648.84(0.15 )
CH 27.95 31.67 (-13.31) 30.37 (-8.66 ) 28.97 (-3.65 )
CH
+
23.00 19.92 (13.39 ) 18.28 (20.52 ) 18.66 (18.86 )
ClH
+
-648.13 -636.67 (1.77 ) -691.30 (-6.66 ) -654.10 (-0.92 )
FH
+
-292.85 -298.68 (-1.99 ) -295.44 (-0.88 ) -265.09 (9.48 )
GaH 289.01
GeH 892.52 931.14 (-4.33 ) 980.24 (-9.83 ) 961.23 (-7.70 )
IH 2523.52 2523.52 (0.00 )
IH
+
-5400.00 -5296.69(1.91 ) -5328.21(1.33 )
InH 711.10 788.83 (-10.93)
NH

-63.00 -56.52 (10.29 ) -55.32 (12.19 ) -59.98 (4.79 )

NH -34.79 -34.33 (1.32 ) -36.54 (-5.03 ) -44.43 (-27.72)
NH
+
77.80 85.73 (-10.19) 87.49 (-12.46) 77.01 (1.01)
OH -139.21 -142.36 (-2.26 ) -141.21 (-1.44 ) -142.36 (-2.26)
OH
+
-83.83 -80.89 (3.51 ) -87.02 (-3.81 ) -76.44 (8.82)
PH -115.71 -117.98 (-1.96 ) -124.43 (-7.54 ) -124.50 (-7.60)
PH
+
295.94 277.76 (6.14 ) 323.01 (-9.15 ) 303.21 (-2.46)
PH

-212.00 -196.69 (7.22 ) -195.27 (7.89 )

RbH 74.57 74.57 (0.00 ) 125.98 (-68.94)
SbH -1574.80 -1541.11(2.14 ) -1373.60(12.78 )
SH -376.96 -380.72 (-1.00 ) -401.01 (-6.38 ) -357.24 (5.23)
SH
+
-216.50 -212.42 (1.88 ) -233.01 (-7.63 ) -219.31 (-1.30)
SeH -1815.00 -1715.25(5.50 ) -1893.81(-4.34 )
SiH 142.83 143.39 (-0.39 ) 156.10 (-9.29 ) 147.97 (-3.60)
SrH 300.00 160.84 (46.39 ) 326.96 (-8.99 )
SnH 2178.88 2297.66 (-5.45 ) 2180.11 (-0.06 )
TeH -3830.00 -3857.09(-0.71 ) -3703.60(3.30 )
Table 2: Fine structure constants of the diatomic hydrides AH,We report the ne structure constant in
cm

1 and the percent of error. The data of MCSCF was taken from Matsunaga et al [koseki], The
DFT data from those reported bi Russo and Chiodo [chiodo] and the ADFT are the calculated ones in
this work. Percent error is calculated from the experimental data.
13
values. 110
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