AYU 292 - 301

About an equilibrium position (T v ) ; the rotation of the molecule as a rigid body about its
center of gravity (T r ) ; onteraction between vibration and rotation (T int ) .

9.8 The Kinetic Energy of a Molecule. It is necessary to obtaion (35) in explicit form before
futher calculations can be made. As shown previosly (T r ) becaome equal to (23), but it
must be remembered of inertia reltive that A, B, ..., F are instantaneous moment and products
of inertia relative to the moving axes. The are not constants but fuctions of the posisition of
the atoms and they change as the mlecule vibrates.

In discussing the therm (T v ) and (T int ) , it is convenient to use normal coordantes (see sec.
10.17). suppose P i has components i/mi , i/mi , i/mi where,

i = lik Qk

i = mik Qk

i = nik Qk

(9-36)

And lik , mik , nik are constant coefficiens such that

lki lkj = 13 ij ; mki mkj = 13 ij ; nki nkj = 13 ij ;

k k k

Then,

mi v2i = (2i + 2i + 2i ) = Q2k

Moreover,

mi (P i x V i ) x = (i i + i i ) = X k Qk

mi (P i x V i ) y = (i i + i i ) = Y k Qk

mi (P i x V i ) Z = (i i + i i ) = Z k Qk

Where,
 X k = (nik mil mik nil ) Ql
i,l

Y k = (lik nil nik lil ) Ql

i,l

Z k = (mik lil lik nil ) Ql

i,l

Collecting terms, (35) finallly appers as

2T t = v 2 mi

2T v = Q2i

2T r = A2x + B2y + C2z 2Dk y 2Ez y 2F x z

2T int = 2x X k Qk + 2y Y k Qk + 2z Z k Qk

9.9. The Hamiltonian Form of the Kinetic Energy. In order to obtain the
Hamiltonian form of (40), we must change form anguler velocities to angular momenta. Form
(17) ot (22) we see that the components of total angular momentum are
T
Px = x
= Ax Dx F x + X k Qk

T
Py = y
= Dx + B x E x + Y k Qk

T
Px = Z
= F x Ex + Cx + Z k Qk

Similarly, the momenta conjugate to Qk are

T
Px = Qx
= Qx X k z + Y k y + Z k z

Solving this equation for Qk and subtituting in (41) gives

P z = Ax Dx F x + X k ( P k + X k z + Y k y + Z k z

With simila expressions for P y and P z . The following abbreviations may be used to simlify
the final result.

A = A X 2k ; D = D + X k Y k

B = B Y 2k ; E = E + Y k Z k

C = C Z 2k ; F = F + X k Y k
In terms of them, we may write

P x = Ax Dx F x + X k P k

P y = Dx + B x E x + Y k P k

P x = F x E x + C x + Z k Qk

if we also write

P x = X k P ki ; P y = Y k P ki ; P z = Z k P ki

(43a) may be futher simplified to read

P x = px Ax Dy + F z

P y = P y Dx + B x E x

P z = P z F x E x + C x

The quantites P x , P y , P z arise from vibration alone as may be seen from ther
definition, eq. (45); the are callled components of internal angular.

Adding together all the terms of (40) and using (41), (42) and (45), we obtain

2T = 2T t + (P x P x )x + (P y P y )y + (P z P z )z + P 2k

Finally, we find by solving (46) for the s thaT

i = ij pj ; (i, j = x, y, z)
j

ij = ji ; P i = (P j pj )

Wiith the use of these variables, eq. (47) takes the more elegant form

2T = 2T t + ij P jP i + P 2k

Explicitly the s are :

B C E 2 AC F 2
xx =
; yy m =

AB D2 C D+ E F
zz =
; yy m =

DE +B F AE DF
xx =
; yy m =
 = | A D F D B E F E C |

9.10. The Vibration Energy of a Molecule.7 - The first term in (47), the translation
energy, is of little interest in physical problems. We shall have no more to say about it. The
only other term of that equaion whitch can be treated futher by classical mechanisc is the last
one, corresponding to the vibrational energy of the Molecule. We first consider the potensial
energy of the system due to the vibration of particles. We fisrt consider the be some fuction
of the mutual positions of the nuclei and it most convenient to specity these in term of the
mass-adjusted component of a displacement vector. We formerly took these as
i / mi, i /mi , i /mi (see eq. 36), 3n in number following convention we now use q 1 , q 2
, ..., q 3n for the same coordibates. If teh system i placted originally in the equilibrium
configuration (all qi = 0 ) and if the particles have very saml
7
This section as well as sec. 9.11 and 9.12 make use of some of the result of Chapter
10. It should be omitted or postponed by readers not familiar eith orthogonal transformations.
The authors suggest that the reader, rather than endeavor to understand normal coordinates by
elementary considerations, acquaint himself with the more powerful methods of the next
chapter.

Initial velocities, we assume that very will never depart to any large distance from tah
configuration, nor will they ever acquire large velocities. Under these conditions, we may
develop the potensial energy V by Taylors theorem in terms of ascending of the qi.

2
V (q 1 , q 2, , q an = V 0 + ( V
q
V
)q i + ( x )qiqj +
i qj
i i,j

The constant term V 0 witch is independent of the q i can be omitted since it has not
effect on the equations of motin of the system. The term linear in the qi must also vanish
since V / q i = 0 is the condition for equilibrium. Finally if the omit all terms beyond the
third, we obtain as an apptoximation to the vibrational potensial energy.

2V = bij q i q j
i,j

Where bij = (2 V /q i q j ). From (37) we have, in terms of the coordinates qi

2T = q2i

Where T os now written for the former T v .

If we now subject both T and V to an arthogonal transformation (see sec. 10.17), we obtain

2T = Q2k ; 2V = k Q2k
Where the normal coordinates Qk are relacted to qs by

q i = aik Qk

The contants k are the 3n eigenvalues found from the eigenvalues

Knowing T and V we may obtain the motion of the molecule by solving Lagranges
equation (8). They appear as
d T V
( )
dt Qk
+ Qk
= 0; (k = 1, 2, , 3n)

Qk = k Qk

Theree different possibliteies arise: (a) k > 0; (b) k = 0; (c)k > 0

a. k > 0. The solutions of (57) are

Qk = Ak cos (k t + k ); (k = 1, 2, , 3n)

This is the equation of simple harmonic motion with two counstants of intergration;
Ak is the amplitude and k , the place constant. Eq (55) now reads

q i = aik Ak cos (k t + k )
k

If all of the Ak are zero expect one, say A1 , then all of the nuclei are acting as simple
harmonic oscillators with a frequency of

1
v1 = 2

About their equilibrium position. Each nucleus has the same phase contants and
reaches its equilibrium position at the same time. The amplitudes will very because of the
factor aik . Such a motion is called a normal mode of vibration. Actually the situtaion is much
more complex, for many of the Ak will be different from zero. This the motion of the nuclei
consists of a superposition of all the normal modes of vibration, each with its own frequency
k /2 and amplitude.
It frequently happens that some of the k will be equal to each other in pairs or
threes. This phenomenon, called double or triple degeneray, 8 means taht two or three
equivalent motions of the molucule have the same frequency and differ only with respect to
their orientation in space. The phase factors and amplitudes must be evaluated from the initial
positions and velocities of the n nuclei. We show in the next section how he normal modes
and coordinates may be determined for a specific example.
 b. k = 0 The solution of (57) is

Qk = Ak t + k

Hence the resulting motion is not a vibration. The nuclei will not oscillate about the
equilibrium position but will continually move away. Since the whole treathment of the
problem is based upon small oscillations from the equilibrium position, we are no longer
justfriend in this case in omitting highher terms in the potential energy energy, and the
method fails. Actually, if will be found that six of the k vanish in the molecular problem
(five if the equilibrium arrangement of he nuclei is linear). Three of these zero frequencies
may be associated with translation of the molecule along three mutually perpendicular axes
and remaining theree with rotation about the same axes. When it is desired, the zero
frequencies may be removed from the problem before solving (56). This is done by reducing
the number of coordinates from 3n to 3n 6, the equations of conservation.

Of linear and angular momentum (qs. 33 and 34) being used for taht purpose.

c. k < 0 . The solution becomes imaginary and again does not correspond to a vibratio.
This case never occurs if the potensial energy is a positive definite quardratic form
(see sec. 10. 12) witch is always true in the molecular problem.

9.11 Vibrations of a Linear Triatomic Molecule. As an examples off the precending

theory, we consider a linear symmetrical triatomic molecule XY2 such
as carbon dioxide. Let
0 0
the central atom X have a massa m2 be x1 for Y and x2 for X. In order to simplify the
problem, we arbitraily assume that the only motion whitch the nuclei can make is laong the
line adjoining them, hence the displaced positions are xi = x0i + X i . If we now take the
potential energy9 as proportional to the square of the relative displacements of the particles, in
accordance with eq. (51) we have
qi q2 2 q2 q3 2
And 2V = k {[ m1
m2
] + [ m2
m1
] }

Comparison with (52), shows us that

b11 = k /m1 ; b12 = b21 = km1m2; b13 = b31 = 0

b22 = 2k/m2 ; b23 = b32 = km1m2; b33 = b33 = 0

When these values are are subtituted in (56) and the determinatal equation is solved we
obtain

1 = k /m1 ; 2 = k ; 3 = 0

= (2m1 + m2 )/m1 m2

In order find the coefficients aik of eq. (55) witch relate thenormal coordinates Qi it
is necessary to find tranformation witch reduces T and V simultaneously to a sum of squares
(see sec. 10.17). According to sec. 10.15 the matrix effecting this transformation has as its
columns the eigenvectors of the matrix bij , and these eigenvectors are the columns the
eigenvector are the solution ( x1 , x2 , x3 ) of the equations

bij xj = xi

Corresponding to the three eigenvalues i already found. Simple computation yields for
these eigenvectors
m1 m2

k
[ x_3, 0, x_3 ] = m1
[x3 , 2 x,
m2 3
x3 ] = k [x3 , x,
m1 3
x3 ] = 0

They are ready orthogonal; when x3 is also fixed by normalization, i.e,. by equating
the sum of the squares of the components of each vector to unity, they may be compounded
to give.

aik = [ 1/2 1/2m1 1/m2 0 2/2m2 1/m1 1/2 1/2m1 1/m2 ]

We can now find the normal modes of vibration from (59). Taking k = 1 , we see
that two end atoms move in opposite directions while the central atom is stationary. The other
normal modes are found in the

Same way. The are shown in Fig.4. It will be observed that the zero frequency10 3 ,
1
the motion is translational, since x1 = m11/2 q 1 = m1 2 a31 (A3 t + 3 ), and x2 , x3 also equal this
exprssion.

The treatment of this molecule is not complete because of the artifical assumption taht
the motion is only along the line of nuclei. For a complete treatment the reader is referred to
Wu, Martihieu, or Herzberg

9.12. Quantum Mechanical Hmailtonian. Lack of scape forbids the transcription of

the result thus far obtained into the quantum mechanical language of Chapter 11. To provide
a general view, however, we shall append of the polyatomic molecule from the quantum
point of view. The material of this section is not needed in other part of this book. The
expression for the classical kinetic energy found in (49) contai momenta P a (a = x, y, z )
defined in eq. (45) and P k defined in eq. (42). Both of these are conjugate to the normal
coordinates Qk . On the other hand the momenta P a of (43) are not the conjugate to Qk . In
other to obtain a suitable expression for use in quantum mechanical calculation, all the
coordinates and momenta must be conjugate to each other. It is true that the P a witch are
fuctions of the angular velocities could be written in terms of some set of coordinates such as
teh Eulerian angles and then the Eulerian angles , , , the normal coordinates and the
conjugate momenta P , P , P , P a and P k would be appropriate. The coordinates used in
(49) may be retained , however, as shown by several authors. The correct quantum
mechanical Hamiltonian is

1 1
H = 1/2 (P a pa )ab 2 (P b pb ) + 1/2 P k 2 + V
a,b k

Where a, b, denote x, y, z and is the determinat of ab . This expression may be

simplified by nothing that P a commutes with P k ant that ab are fuctions only of the Qk .
We this obtain

1 1 1 1
H = ab P a P b ha P a + 2 pa ab 2 pb + 2 P k 2 P k + V
a,b a,b

Where

1 1
ha = 2ab P b + pb ab 2 (pb 2 )
b

and pb does not commute with the s .

For the sake of greater generality, we no longer need confine ourselves to the
potential energy expression previously used but write the most general function consitent
with the symmetry of the molecule.

V = V0+ V1+ V2+

The first term, V 0 , is indetical with that given in (52) or (54) ; V 1 is homogeneous in
the third powers of the normal coordinates and their crossproducts; V 2 is f he fourth power,
etc. When he Hamiltonian is expanded, it is found taht it can be divided into terms of
different orders as follows:

H = H0 + H1 + H2 +

Teh expicit form of H 0 is

p2 py2 pZ2
2H 0 = { Ax + B0
+ C0
} + P 2k + V 0
0

Where A0 , B 0 , C 0 are the equilibrium mment of inertia. It i seen that this represent
the sum of the Hamiltonians of a rigid rotator and a harmonic oscillator; hence this part of H
ay be treated exactly by the method of quantum mechaniacs as outlined in Chapter 11.

Even to this order of approximation the details are tedious, for the vibrational part of
the Hamiltonian for an n-atomic molecule involves the solution of molecular systematry,
however, makes it possible to factor pressed in coordinates parallel or perpendicular to
chemical bonds (so-called vallence-bond coordinates), then vector and matrix methode ,
develoved by Wilson and other, prove to powerfull tool for even quite complex moleculales

Still futher difficulties aries if higher terms in the Hamiltonian are included but these
are important if interactions between the rotational and vibrational energies are considered.
Such intercations are often detectable especially in the microwave region. A suitable
perturbation technique for such cases, witch involves contact transformations, has been
applicated to many special moleciles.
 CAPTER 10

MARTICES AND MATRIX ALEBRA

In ordinary arithmetic, attention is focused upon single numbers. These numbers may
be combined by various operation, such as addiction, subtraction, multipcation and so on, to
yield new numbers. In many branches of algebra, the student is forced to confer interest, not
upon single numbers, but on collections of numbers (or functions). These collections can be
simple sequences is written down, no understanding collection itself whitch matters. Meaning
is imparted to the collection by specifying how it is to combined with other collection.

Besides simple sequences, collection of two-dimensional character are ofthen object

of interest in mahematical, and recently in physics and chemistry. They may have a great
variety of forms; they may be tri-angular, as

a1 b1 b2 c1 c2 c3

Or rectangular, as

a1 a2 a3 an b1 b2 b3 bn .. .

e1 e2 e3 en

Or quadratic, as

a1 a2 a3 b1 b2 b3

c1 c2 c3 d1 d2 d3

Of these, the rectangular and quadratic ones are of greathes value. Without futher
specification, theye are simply arrays, devoid of meaning. But when rules are laid down,
stating how they many may be combined to form new arrays, then become object of
mathematical importance, such us

Vio 312-321
In terms of this,
yX x=Yx

The vectors u1 u2, ..., un are linearly independent if there exists no set of scalar quantities c1,
c2,...,cn not all zero such that

c2,u2+...+cnun =
c1u1 + 0 (10-13)
The simplest way of testing vectors for linier independence is to evaluate the Gram
determinant (see sec. 3.13)
|r| = [u1 u1 u1 u2 u2 u1 u2 u2 u1 un u2 un un u1 un u2 un un ]

If |r| vanishes, the vectors are linearly dependent: if |r| > 0, linearly independent.
When n linearly independent vectors have been chosen they form an n-dimensional
coordinate system or basis, being equivalent to a set of n coordinate axes. Any other vector v
may then be expressed as a linear combination of the chosen vectors u1, u2,...,un the linear
combination being unique. It should be empasized that there is nothing unique abaout the
choise of the basis, for any n linearly independent vectors are suitable for that purpose
although the most convenient choise, in general, is a set of unit vectors. The letter are defined
1
by he relations
e1 = {1, 0, 0, 0, , 0}

e2 = {0, 1, 0, 0, , 0}

e3 = {0, 0, 1, 0, , 0}

en = {0, 0, 0, 0, , 1}

or similarly as row vectors. Clearly they are of unit length and mutually perpendicular, for
ei ej = ij (10-14)

In terms of the unit vectors, any vector x may be written

X = x1e1 +
x2,e2+...+xnen =
0 (10-15)
If the origin of x is taken as coincident withh the origin of the basis formed by the ei, the
components of x are the coordinates of the terminus of x.
It is often necessary to use a particular set of linearly independent vectors as a basis,
constructing from them a set whise members are mutually perpendcullar and of unit length.
This procedure, known as Schidts orthogonalization method, is effected in the following
way. Suppose the n given vectors are u1, u2,...,un. Select any one of them, say u1, and let v1
=u1, e1 = v1/l1, where l1 is the lenght of v1. Now take v2 = u2 c21e1, choosing c21 so that
1 u2 )e1 . If we put e2 = v2/l2, where l2 is
= 0 which requires c21 = e1u2 or v2 = u2 - (e
e1 v 2 = e 1 u2 c21 e 1 e 1

the lenght of V2, we shall have e1 e2 = 12 . Next let v3 = u3 c31e1 - c32e2, determining the
constants so that e1 v 2 = e 1 v 3 c31 = 0 and e2 v 3 = e 2 u3 - c32 = 0, which means that c31 =

1
Notice that the subscripts on the vectors ei do not designate components.
e1 u3 and c32 =
e2 u3 . Finally
let e3 = v3/l3. Continuing in this way, we may construct the
complete set of n unit vectors with
n
v n +1
en+1 = ln +1
; v n+1 = un+1 (e k un+1 )ek
k=1

Problem a. Consider the columns of the matrix of problem, sec. 10.5, as the components of four
vectors. Test them of linear dependence.

Problem b. Prove that Y3 = - [y]{y}Y. This relation is known as the Cayley identity.

10.9 Linear Equations. Matrix methods are useful in solving and discussing linear
equations of the form

A11 x1 + A12 x2 + + A1n xn = y 1

A21 x1 + A22 x2 + + A2n xn = y 2

An1 x1 + An2 x2 + + Ann xn = y n (10 16)

2
Which are inhomogeneous . They may also be written as

Ax = y

The corresponding homogeneous equation is

Ax = O

The marix A and the vector y are to be considered as known while the n comoponents of x
are unknown. The questions of chief interest concern the number of possible solutions and
the method of finding them. Several cases arise depending on the rank of A, ut for our
3
purposes we consider only theree possibilities.

a. y 0; |A|0. According to (10), A-1 exists, hence

Ay
x = A1 y = |A|

is the unique solution. From the definition of A and the rule for matrix multiplication, it also
follows that

2
See sec.2.5 for the meaning og the term homogeneous
3
The others are discussed by Bocher, M., Introduction to Higher Algebra, Macmillan Co., New York, 1907.
 xi = 1
|A|
(y 1 A1i + y 2 A2i + + y n Ani )
4
which is commonly known as Cramers rule

b. y = 0 ;|A| 0. The only solutions are the trivial ones 1 = 2 = . . . = n = 0.

c. y = 0 ; |A| = 0 ; Aik 0 for at least one value of i and k . If we knew the value of one
of the unknowns we could find the values of the remaining ( n 1 ) unknowns, since we
could the form from the original set ( n 1 ) inhomogeneous equations with non-vanishing
determinant. In other words, we are confronted in case (c) with n unknowns but only ( n 1 )
equations. However, we note that the k-th row of our set of n equation is

Ak22 +
Ak11 + . . . + Aknn =
0 (10-17)
so that if we take
i =
cA
ji
(10- 18)
where c is any constant, it follows from (3) that (17) is satisfied. Even if j = k, we still have
a solution, for (17) is then identical with (2) but |A| = 0. We thus have an infinite number of
solutions of the homogeneous equation when |A| = 0 as j may take any value from 1 to n and
c is completely arbitrary. Of course, some of the solutions (18) may be worthless, since
several of the cofactorsmay vanish ; but it will be found that there are always enough
5
non-vanishing ones so that the ratio of all the unknowns is determined The fact that the set
of homogeneous equations Ax = 0 possesses non-trivial solutions only when |A|= 0 is of great
importance in many problems and will often be used in the next chapter.
Problem a. Sometimes chemical analysis must be don in an indirect way. Solve the
followinf problem by means of determinants. A mixture of sodium chloride, sodium bromide,
and sodium iodide weighed 0.5000 gram. Upon the addition of silver nitrate, the mixed silver
halides weighed 1.0369 g. The iodine in the mixture was precipitated as palladous iodide,
which weighed 0.3006 g. Find the composition of the original mixture .
Ans. NaCl, 50%; NaBr, 25%, NaI, 25%.
Problem b. Solve the set of linear equations which result from application of
Kirchoff's laws to the network known as a Wheatstone bridge, out of balance, and obtain the
current through the galvanometer. Label resistances R1, R2, R3, R4, going
clockwise around the
" diamond." Let galvanometer resistance be Rg.

4
In actual calculations, it is usually simpler to solve (16) by direc elimination (cf.sec.13.26).
5
The proff is given by Bocher, p.4.
 (R2R4 R1R3) E
Ans ig = R1 R2 R3 +R2 R3 R4 + R3 R4 R1 + R4 R1 R2 + Rg (R1 +R2 )(R3 +R4 )

where E is the external electromotive force.

10.10 Linear Transformations. Consider a set of linear, inhomogeneous
equations, similiar to (16), relating m quantities x and h quantities x', which can be written
in the form

xs = B sq xq ; s = 1, 2, , h; q = 1, 2, , m (10 19)
q

These equations define a linear transformation , which may be inerpreted in two different
ways, as we shall see later.

Furthermore, let n quantities x be rrelated to x :

xp = Aps xs ; p = 1, 2, , n
s

Then, on combining these equations, we find

xp = Aps B sq xq
s,q

The same equations could also be written as a single sum

xp = C pq xq (10-20)
q

provided that we agree to take Cpq as in eq. (6) which dfines the law of matrix muliplication.

The importance of linear transformations thus ndicates that this definition ofmatrix
multiplication would be useful o ne. It could , of course, be defined in others way, and one
possibility is

(AB)ik = Aij B
kj

where, for convenience, the summation sighn is omitted and summation over the repeated
index, as in tensoranalysis, is required. The consequence of this definition is interesting, for if
we multiply by a third matrix C, we find

(AB. C)ik = (AB)ik C kj = Aik B js C kj

but

(A.B C)ik = Ais (BC)ks = Aik B js C kj

and the matrix elements are not the same in the two cases. Therefore. The associative law of
multiplication would not hold.

A liniear transfomation is frequently interpreted as a rotation of coordinates axes. In

sec. 4.1, we have shown how direction cosins may be used to relate the components of a
vektor in two different coordinate systems. Let us now consider these relations in matrix
notation. Suppose that two system OXYZ and OXYZ, or bases with unit vectors e and e,
coincide originlly and that OXYZis then rotatedin the positive(counterclockwise) direction
through the angle about the OZ-axis. A vectoe x in the new system is related to te same
vector x in the original system by an equation similar to (19), which in matrix form would
read

X = B ( )x (10-19a)

Rotate the system again, tis time through the angle , to obtain OXYZ and the vector
becomes x, where X = A ( )x. We could then write

X =Ax = Abx =Cx (10-20a)

from which we see that C = AB is a matrix which transforms x directly to x, without

passing through the intermediate system in which it was called x. We also see form (20a)
that, if physical significance is to be attached to the matrices A and B, he order of performing
the operations involved must be preserved, for in general AB BA although the matrices do
commute, in the case now being discussed. As suggested by this exmple, we always
6
understand that the order is from right to lrft, B first and then A in the case of eq. (20a)

Provided C is not singular, we may find C-1 , hence

C 1 x = C 1 C x = x (10-21)

6
The opposite convention is often used and endless confusionn may resul if this fact is overlooked when the
equations of various writers are compared. The elements of the matrix products, of course, must always be
evaluated from left to right, as required by eq.(6)
We may thus use (20) or (21) to determine the components of the same vector in either of two
different coordinate systems.

Sometimes one wishes to think of linier transformations in another way. Suppose that
there is only one coordinate system and that a vector x isrotated trough the angle in the
negative (clockwise) direction . he matrix elements will therefore not be identical with those
used when we assume two different coordinate systems. They are, however, closely related
as will be shown in sec. 10.17.

10.11 Equivalent Matrices.Let P and Q be non-singular matrices. Then A and B

are said to be equivalent when

B = PAQ (10-22)

Equivalent matrices have many properties in common as the subsequent discusion will show;
heir importance is due to the fact that it is often possilbe by means of a linear transformaion
like (22) to find an equivalent matrix which has simpler properties than the original one.
When the equivalent matrix is in its simplest form, usually diagonal, it is said to be canonical.
7
The problem of finding an equivalent matrix of canonical form is analogous to tht of
finding a suitable coordinate system in ordinary scalar algebra (cf. Chapter 5)

Several special cases of equivalent matrices are possible, depending on the nature of the
matrices P and Q efffecting the transformation.

a. If PQ = E, then
B = Q1 AQ (10 23)

The transformation is called collineatory or a similarity transformation

(ahnlichkeitstransformation). The two matrices A and B are said to be the transforms of each
other.
b. If P = Q , the transformation is called congruent:

B = QAQ (10 24)

c. If P = Q , then
B = Q AQ (10-25)

Canonical matrices are exhaustively discussed by Turnbull, H.W., and Aitken A.C.,The Theory of Canonical
7

Matrices, Blackie and Son, London, 1932

The transformation is conjunctive. If the matrices are all real; this becomes identical with
(24)
d. If PQ = E, P = Q (i.e., Q is orthogonal) and all the matrix elements are real, then

B= Q AQ = Q1 AQ (10-26)
represents a real orthogonal transformation . It is both collineatory and congruent
e. If the matrix elements are complex and PQ = E, P = Q = Q1 (i.e., Q is unitary) then
B = Q AQ = Q1 AQ (10-27)
is called a unitary transformation . It is collineatory and conjuctive.

10.12 Bilinear and Quadratic Formsa homogeneous polynomial of the second

degree in 2n variables x1 x2 ,..., xn ; y 1 , y 2 ,..., y n is called a bilinear form. It may be
abbreviated as
n
A(x,y) = x Ay = Aij xi y j (10-28a)
i,j

Where A = [Aij]. If both x and y undergo non-singular transformations

x = Px ; y = Qy
Then
A(x,y) = xP AQy = xBy = A(x.y ) (10 29)
If P = Q1 , so that x = Q1 x ; y = Qy then x and y are called contragradient variables
since they undergo opposite transformations.
As a spesial case of a bilinear form suppose x = y. Then tge coefficienr of xi xj (i j)

in (29) is (Aij + Aji )/2 , and the matrix A becomes symmetric if we write for every

(Aij and Aji .Eq.(28a) may then be written

n
A(x,x) = Aij xi y j = x Ax; A = A (10-28b)
i,j

Such a function is a quadratic form; if it is positive for all real values of the variables, it is
called a positive definite quadratic form; if it is positive or zero, it is called semi-definite
10.13 Similarity Transformations--- Suppose the same vector is called x when
referred to the basis e and x when reffered to another basis e. Let another vector be y or y,
where
X = Qx ; y = Qy (10-30)
Such variables which undergo the same transformation are said to be cogredient. Now
consider the transformation
X = Ay (10-31)
Which changes y into x in the basis e. Then,
Qx = Ay = AQy
or, if Q is non -singular
X = Q1 AQy = By (10-32)
Hence , (32) is a transformation which changes y into x in the basis e while A, the
transform of B, perform the corresponding transformation from y to x in the basis e. This is
the reason for the name similaritt transformation.
An alternative interpretation of the transfom ay b given. Let x, x, y, y be four
different vectors all in the same basis. Then (30) changes x into x and y into y while (31)
changes y into x. The single transformtion that changes y directly into x is (32), since x =
Q1 x = Q1 A = Q1 AQy. Here as in sec.10.10, the form of the matrix equations is
similiar for different refenrences vectors in the same basis or the same vectors in diferrent
reference frames. The matrix element , however, will not be identical in the two cases.
10.14 the characteristic Equation of a Matrix.--- If is a scalar parameter, A is a
square matrix of order n and E the unit matrix of the same order, the matrix
K = [ E A] (10-33)

is called the characteristic matrix of a. The equation

K() = |K|= |E - A| =0
or its equivalent
K( ) = n + a1 n-1
+ a2 n-2
+ ... + a2 = 0 (10-34)
Where the a s kecil are function of the elements of A, is the characteristic equation of A.
The n roots of K (), 1, 2, 3,.., n not necessarily all different, are the characteristic (or
lalent)roots. On writing (34) in the form
( - 1) ( 2) ( 3) ..... ( n) = 0
And comparing coefficient of the powers of it will be seen that

2 +
1 + ... + n = - a1
1 2 + 1 3 +....+ n-1 n = a2
 1 2 3 +...+ n-2 n-1 n =
- a3

..........................................................................................

1 2 3 ... n =
(-1) an
n

If B = Q1 AQ , then [E B ] = [E Q1 AQ] = Q1 [E A]Q

Moreover,
|E B | = |Q1 ||E A||Q| = |E A| (10-35)
Hence two matrices related by a similarity teansformation have the same characteristic roots.
We leave the proof of the following statements to tge reader
Tr Q1 AQ =Tr A
|Q1 AQ| = |A|

If C = A x B, the characteristic roots of C are the products, taken in pairs, of the roots of A
and B
Problem . Prove rhe statements of the preceding paragraph
10.15. Reduction of a Matrix to Diagonal Form.--- Consider the linear
transformation
Ax = x (10-36)

The only effect of the matrix A on the vektor x is to multiply it by the constant scalar
factor . Rewriting (36) in the form
[E A]x = K x = 0 (10-37)
We see that, except for the trivial case where all the components of x are zero, |K| must
vanish (cf sec.10.9b,c). Hence , as shown in the previous section, can only take the values
1, 2,..., n where i is one tge charactwristic roots of K (). These quantities are the
eigenvalues of the matrix A; the accompanying sets of vectors x are the eigenvectors.Eq (36)
is the matrix form of an eigevalue equation, otger examples of which were discussed in
Chapter 8.
Now suppose B is a diagonal matrix; then the roots of its characteristic equation are
identical with its diagonal elemwnts. If A is not a diagonal matrix but is related to B by a
similiarity transformation, B = Q1 AQ, then it follows from (35) that its characteristic roots
an equation are the same as rhose of B. The problem of reducting A to diagonal from by
means of a similiarity transformation is thus closely related to the problem of finding its
eigenvalues. We shall now show how such a reduction may be made.
8
The eigenvalues themselves must first be obtained by solving (34).
Having found the lamda i, we wish to determine a matrix X such that
X-1 AX = = [i ij ] (10-38)

We distinguish the following two cases

a. The Eigenvalues are all Different. Let us consider the case in which all eigenvalues
of A are different. Select one, say k, and form the n linear equations
Ax = k (10-39)
They are homogeneous, but as shown in sec.10.9 we may solve them for the ratio of the
components of thw eigenvector xk. Remembering that each component contains an arbitrary
constannt, we wrire them as a column vector
Xk = {x1k, x2k, ...., x nk }
The remaining eigenvectors are determined in thw same way using each eigenvectors of A.
This matrix clearly satisfies the equation.
AX = X [i ij]
When this result is multiplied by X-1, eq(38) is obtained. We have thus shown thatthe matrix
X which diagonalizes A, may be found by compounding the eigenvectors of A into a matrix.
The reduction to diagonal form here described is unique expect for the order in which the
eigenvalues occur along the diagonal.
Although not required by the method, the eigenvectors may be orthogonalized and
normalized by the Schmidt process, which fixes the undertermined constand appearing in the
solution of (39). We return to this question in sec. 10.17
b. The Eigenvalues are Not all Different. When two or more of the eigenvalues of A
are equal to each other, reduction to true diagonal form is not always possible. Suppose 1 is
an eigenvalues of A repeated r1 times. Proceeding as before, we find an eigenvector x1 so that
Ax1 = 1 x1
Then if x1 is the first column of a square matrix X , the first column of AX will be 1x1 and
the first column of X-1 AX will consist of 1 followed by (n-1) zeros. Call this matrix B
B = X 1 AX = [1 B j 0 B ij ]; i, j = 2, 3, , n

8
Numerical methods of finding then are discussed in sec. 13.28.
Here Bj, is a row matrix with (n-1) elements and Bij is square of order (n-1). Since B is the
transform of A, it also has the eigenvalues 1 repeated r1 times, but Bij contains that
eigenvalue only (r1 - 1) times. The matrix is subjected to the same procedure as A : we find an
eigenvector and form a new matrix Y whose first column is that eigenvector. Note however
that Y has only (n-1) rows and columns and
Y 1 B ij Y = [1 C k 0 C kl ]; k , l = 3, 4, , n

so that the matrix

|1 0 0 Y |

will transform B into the form

[1 B j Y 0 1 C k 0 0 C kl ]

Continued applications of similiar transformations will eventually result in a single

matrix Z such that
Z 1 AZ = [A1 F 0 G ] (10 40)

Where
A1 = [ 1 H 12 0 1 0 0 H 13 H 1r1 H 23 H 2r1 1 H 3r1 00. . . 1 ] (10 41)

The matrix F is rectangular with r1 rows and (n r1) columns while G is square and of order
(n r1). Now if Z1 is
a rectangular matrix composed from the frist r1 columns of Z, then
e may
remove the unwanted matrix F from (40), for
Z1-1AZ1 = A1
The next steps is to treat the matrix G in a similiar way until it is reduced to the form
of A1, with its eigenvalue 2 along the diagonal. We then continue with each remaining
matrix until every eigenvalue has been used. Finally if we join together all of the rectangular
matrices Zi to from a aquare matrix Q, we will have
W-1 AW = diag (A1, A2, ... Ar)
where r is the number of distinct eigenvalues of A. Note that we are using the notation of sec.
10,7 to denote a diagonal matrix, but in this case the diagonal elements Ai are really matrices
themselves. Each is of the triangular from of (41)
In the geeral case it is possible to make a further transformation so that the eigivalues
occur along the diagonal of Ai, while unity appears in