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Chem3023 Note On Sums

This document discusses orthogonality and sums in quantum chemistry expressions. It defines orthogonality of wavefunctions as having an overlap integral of 0 when i ≠ j. Sums are used to compactly write linear combinations of molecular orbitals. A double sum is required to write the overlap integral of such a linear combination, simplifying to a single sum when the molecular orbitals are orthonormal due to their orthogonality. Exercises are provided to rewrite the equations using bra-ket notation and determine a normalization constant.

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Chris Skylaris
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111 views

Chem3023 Note On Sums

This document discusses orthogonality and sums in quantum chemistry expressions. It defines orthogonality of wavefunctions as having an overlap integral of 0 when i ≠ j. Sums are used to compactly write linear combinations of molecular orbitals. A double sum is required to write the overlap integral of such a linear combination, simplifying to a single sum when the molecular orbitals are orthonormal due to their orthogonality. Exercises are provided to rewrite the equations using bra-ket notation and determine a normalization constant.

Uploaded by

Chris Skylaris
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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CHEM3023 course note: Orthogonality of wavefunctions

and sums in quantum chemistry expressions


Chris-Kriton Skylaris
School of Chemistry, University of Southampton
February 4, 2010

1 Orthogonality
• The overlap integral between two wavefunctions ψi (r) and ψj (r) is defined as
Z
ψi∗ (r)ψj (r)dr = Sij (1)

where Sij is the value of the above integral.

• We say that wavefunctions ψi (r) and ψj (r) are orthogonal if Sij = 0 when i 6= j.

• We say that a wavefunction ψi (r) is normalised when Sii = 1.

• Wavefunctions that are normalised and orthogonal are called orthonormal. In this
case we can write Z
ψi∗ (r)ψj (r)dr = δij (2)

because the symbol δij (which is called the Kronecker delta) is defined to have the following
property: (
1 when i = j
δij = (3)
0 when i 6= j

2 Sums
Let’s assume we have a function f (r) which is a linear combination of five molecular orbitals:

f (r) = c1 ψ1 (r) + c2 ψ2 (r) + c3 ψ3 (r) + c4 ψ4 (r) + c5 ψ5 (r) (4)

where c1 , c2 , c3 , c4 and c5 are coefficients (i.e. numbers). We can represent this in a much more
compact way by using a summation symbol
5
X
f (r) = ci ψi (r) (5)
i=1

1
3 Double Sums
Let’s try now to evaluate the overlap integral of f (r) with itself. We have:
Z Z X
5 5
X 5 X
X 5 Z
∗
f (r)f (r)dr = c∗i ψi∗ (r) cj ψj (r)dr = c∗i cj ψi∗ (r)ψj (r)dr (6)
i=1 j=1 i=1 j=1

Note that:

• Using a double sum is the only practical way to write the above expression. Otherwise
we would need to write each term explicitly and we would need to include 5x5=25 terms!

• Notice that the two sums have different indices i and j. This is necessary in order to be
able to distinguish the terms that belong to the first summation from those that belong
to the second summation.

Now let us assume that the molecular orbitals in equations 4 and 5 are orthonormal. Then the
double sum of equation 6 is simplified to a single sum:
Z X 5
5 X Z X 5
5 X 5
X 5
X
f ∗ (r)f (r)dr = c∗i cj ψi∗ (r)ψj (r)dr = c∗i cj δij = c∗i ci = |ci |2 (7)
i=1 j=1 i=1 j=1 i=1 i=1

This simplification is a consequence of the orthogonality as the integrals with i 6= j are equal
to zero.
Note that in the above examples we used 5 terms in each sum but this was a random choice.
For example, in many of the quantum chemistry expressions we have seen so far there are sums
that contain Nelec /2 terms, where Nelec is the number of electrons in a molecule.

4 Exercises
1. Re-write all of the above equations in bra-ket notation.

2. If F (x) is a function which is not normalised, find by what number you need to multilply
it to make it normalised. This number is called a normalisation constant.

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