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Matrix Representation in Quantum Chemistry

Matrix representations provide a way to express quantum wavefunctions and operators using linear algebra. A wavefunction can be written as a column vector of coefficients corresponding to an orthonormal basis set. Operators acting on wavefunctions are represented by matrices, where matrix elements are the operator acting on basis functions. For a complete basis, matrix multiplication replaces operator ordering, allowing the calculation of expectation values and transformations between basis function representations. Finite basis sets used in approximate quantum chemistry methods introduce errors not present in complete basis representations.

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Fredrick Mutunga
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185 views4 pages

Matrix Representation in Quantum Chemistry

Matrix representations provide a way to express quantum wavefunctions and operators using linear algebra. A wavefunction can be written as a column vector of coefficients corresponding to an orthonormal basis set. Operators acting on wavefunctions are represented by matrices, where matrix elements are the operator acting on basis functions. For a complete basis, matrix multiplication replaces operator ordering, allowing the calculation of expectation values and transformations between basis function representations. Finite basis sets used in approximate quantum chemistry methods introduce errors not present in complete basis representations.

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Fredrick Mutunga
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  • Matrix Representation of Wavefunctions
  • Operators in Matrix Form
  • Application Example with Operators
  • Operator Identity Resolution

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*

2
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

4
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.

Matrix Representation of Wavefunctions and Operators in Quantum Chemistry The following is a consequence of expanding a ge
2 For the overlap integral between Ψa and Ψb : Ψa Ψb = ak * φk φl bl l∑ k∑ = ak *bk = a k∑ † ⋅b Thus integration in t
3 Consider a 2nd operator ˆB acting on Ψb to yield another function Ψc that can be represented by the vector c in our ba
4 The unit operator (resolution of the identity) in a complete basis set: ˆI = φk φk k∑ leads to the unit matrix I

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