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Variation Methods

The document discusses the variation method used to approximate solutions to the Schrödinger wave equation for multi-electron systems. It outlines the steps involved in choosing a trial wave function, calculating average energy, and applying the variation theorem, which states that the expected energy from the trial function is always greater than the true ground state energy. Additionally, it explains the significance of energy eigenvalues and their probabilities in determining the average energy of the system.

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9 views12 pages

Variation Methods

The document discusses the variation method used to approximate solutions to the Schrödinger wave equation for multi-electron systems. It outlines the steps involved in choosing a trial wave function, calculating average energy, and applying the variation theorem, which states that the expected energy from the trial function is always greater than the true ground state energy. Additionally, it explains the significance of energy eigenvalues and their probabilities in determining the average energy of the system.

Uploaded by

swatantrakumargond
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

1

2
The variation method
For 1 e- system, it is easy to obtain solution of Schrodinger wave equation, but for 2 e- system, the solutions is tedious
and we use approximation methods

Perturbation method
•1st, 2nd, 3rd order

Variation method
•Linear or non-linear
4
VARIATION METHOD
A simple hit and trial method involving following steps:

1. We decide or chose a trial wave function and it is assumed to be solution of Schrodinger wave equation.
2. After deciding the trial wave function we calculate the average energy by postulates of quantum mechanics
using the following:

3. The calculated average energy must be minimum, i.e. we can apply the concept of minimization of energy
𝜕𝐸
=0
𝜕𝑎

VARIATION THEOREM

The expected energy or the average energy calculated from trial wave function is always greater than true
value/exact value/ground state value (E0)

1
5
6
2

7
5

8
2. The energy associated with linear combination function as shown in equation 2 is the weighted average of the
energy eigenvalues of equation 3 and this average energy is calculated as:

Suppose

9
So equation 9 becomes:
10

Now we subtract Eo (the lowest energy from both sides), we get

11

12 10
12

Since Eo is the lowest energy of the system, so E1 > Eo and E2 > Eo, while
a12 and a22 are always positive
ത
OR 𝐸 > 𝐸0

The significance of equation 10 is that if energy of the system is


measured at any instant, it will be either of the two eigen values E1 and
E2 , with probabilities a12 and a22 , respectively and the average energy E
will be given by equation 10

10

11
12

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