Matrix Representation of Wavefunctions and Operators in Quantum Chemistry

The following is a consequence of expanding a general wavefunction in a complete set of

eigenfunctions
For a complete, orthonormal basis set {n } , i j = ij

For general state functions a and b, one can then exactly write:
a = k ak
k

b = l bl
l

Furthermore, for a specified basis set it is sufficient to know just the coefficients ak in
order to calculate the function a at any given point. The function a can then also be
completely specified by the column vector

a=

a1

a2

an

By analogy, the function b can be represented by the column vector b.

The norm of the function a is the same as the absolute square of the vector a :

a a = ak* k l al
k

= ak*ak = a a = a

where a , the adjoint of a, is the row vector

a =

(a

*
1

a2* an*

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For the overlap integral between a and b :

a b = ak* k l bl
k

= ak*bk = a b

Thus integration in this basis representation will be replaced by a scalar or inner product.

to a results in the function b :

Now assume that application of some operator A

b = A
a
In terms of our basis set,

a
b = l bl = A
k
k
l

A particular coefficient bn in the definition of b is obtained by multiplication on the left

by n :

l bl = bn
a
= n b = n A
k
k
= Ank ak

or in matrix notation: b = A a

becomes the matrix A in the basis representation with matrix

Thus the operator A
elements Aij, and the effect of an operator acting on a function is transformed to a matrixvector multiplication.
A hermitian operator corresponds to a hermitian matrix with the property

Aij = A*ji
or A = A

acting on b to yield another function c that can be

Consider a 2nd operator B
represented by the vector c in our basis:

=B
A
c = B
b
a
expansion gives:
b
c = i ci = B
l
l
i

a
= B l l A
k
k
l

The coefficients cj are obtained by multiplication on the left with j :

c j = j c
a
A
= j B
l
l
k
k
l

= B jl Alk ak

which in matrix notation is:

c = Bb = BA a

becomes the matrix product B A in the matrix

A
So the operator product B
representation.
Of course all of the above is strictly valid only for complete basis sets. For a finite basis
M

B
B
A
. The usage of finite basis sets in
set of M functions, i A
j
i
k
k
j
k 1

approximate methods of quantum chemistry will be discussed later in this course.

Expectation values in the matrix representation
= a* A
a
a A
a
k
k
l
l
k

= a A a

Matrix element of A
= a* A
b
a A
b
k
k
l
l
k

= a Ab

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The unit operator (resolution of the identity) in a complete basis set:

I =
k
k
k

leads to the unit matrix I :

I ij = i I j = i k k j = ij
k

Acknowledgements:
This document is a poor translation of the original lecture notes in German prepared by
Prof. Dr. H.-J. Werner, Institut fr Theoretische Chemie, Universitt Stuttgart. Any
errors are solely the product of the present author.