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The Variation Method

The document discusses the variation method for approximating solutions to the Schrodinger equation. It describes taking a trial wave function with parameters and optimizing the parameters to minimize the calculated energy and obtain a better approximation. As an example, it shows using a trial wave function for the hydrogen atom. It also derives the secular equations that result from applying the variational principle to a linear combination of basis functions with coefficients to be optimized. Solving the secular equations determines the optimal coefficients and approximated energy.

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46 views3 pages

The Variation Method

The document discusses the variation method for approximating solutions to the Schrodinger equation. It describes taking a trial wave function with parameters and optimizing the parameters to minimize the calculated energy and obtain a better approximation. As an example, it shows using a trial wave function for the hydrogen atom. It also derives the secular equations that result from applying the variational principle to a linear combination of basis functions with coefficients to be optimized. Solving the secular equations determines the optimal coefficients and approximated energy.

Uploaded by

skc3128
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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Lecture 14

The variation method

An exact solution of the Schrodinger equation is possible only for a one electron system. In larger
systems, approximate methods have to be used. There are two kinds of approximate methods, the
perturbation method and the variation method. The latter method is more useful in chemical
bonding.

The wave equation is,

∇2ψ + 8π 2m/h2 (E – V) ψ = 0

We can rewrite this in the familiar form,

(-h2/8π 2m ∇2 + V) ψ = Eψ

The quantity in the parentheses is an operator, H.

Thus,

Hψ =E ψ

Let us integrate within the space of the wave function.

∫ψ*Hψ dτ = E ∫ψψ* dτ

or

E = ∫ψ*Hψ dτ / ∫ψψ* dτ

Thus, if the wave function is known, we can get the energy. Although it is possible to get the exact
form of H, it is difficult to get the exact wave function. Still, the method is useful in getting the
approximate wave equation.

If we have the correct wave function we have the correct energy. But, often we do not have it.
Variation theorem says that if we have a trial wave function ψi, the energy Ei we get from the
equation above will be higher than the true energy Eo. This principle can be used in determining
the best trial function and can be used further to improve the function. One can actually write the
wave function in terms of certain parameters and can optimize the parameters to get the minimum
energy.

The variation principle can be demonstrated using the hydrogen atom. One can take the trial wave
function of the form, ψ = e -ar. Using the right H, we can show that we get the right energy.
The Secular Equations

The trial wave function can be complex. It may be in the form of functions, ϕi, the coefficients, ai
are arbitrary.
ψ = a1ϕ1 + a2ϕ2 + . . . + anϕn

We can take a simple function,

ψ = a1ϕ1 + a2ϕ2

The energy,

E = ∫ (a1ϕ1* + a2ϕ2*) H (a1ϕ1 + a2ϕ2) dτ / ∫ (a1ϕ1* + a2ϕ2*) (a1ϕ1 + a2ϕ2) dτ

Or

E ∫ (a1ϕ1* + a2ϕ2*) (a1ϕ1 + a2ϕ2) dτ = ∫ (a1ϕ1* + a2ϕ2*) H (a1ϕ1 + a2ϕ2) dτ

Which leads to,

E ( a12 ∫ ϕ1*ϕ1 dτ + 2a1a2 ∫ ϕ1*ϕ2 dτ + a22 ∫ ϕ2*ϕ2 dτ ) = a12 ∫ ϕ1*Hϕ1dτ

+ 2a1a2 ∫ ϕ1*Hϕ2dτ + a22 ∫ ϕ2*Hϕ2dτ

The equation, ∫ ϕ1*αϕ2 dτ = ∫ ϕ2α ϕ1* dτ is not always right for all operator, α. This will be valid
only for Hermetian operators. The eigen values are always real.

We need to have minimum value for E. Thus, energy should be minimized with respect to a1 and
a2.

Differentiate with respect to a1.

E [ 2a1 ∫ ϕ1*ϕ1dτ + 2a2 ∫ ϕ1*ϕ2dτ ] + ∂E/∂a1 [ a12 ∫ ϕ1*ϕ1dτ + 2a1a2 ∫ ϕ1*ϕ2dτ + a22
∫ ϕ1*ϕ2dτ ] = 2a1 ∫ ϕ1*Hϕ1dτ + 2a2 ∫ ϕ1*Hϕ2dτ --- Eq (1)

In order to minimize energy, we need

(∂E/∂a1)a2 = (∂E/∂a2)a1 = 0

Let us use,

Hij = ∫ ϕi*Hϕjdτ and Sij = ∫ ϕi*ϕj dτ

Let us assume ∂E/∂a1 = 0, in eq. 1. Then we can write,


(H11 – ES11) a1 + (H12 – ES12) a2 = 0

For a similar condition, ∂E/∂a2 = 0, we can get,

(H21 – ES21) a1 + (H22 – ES22) a2 = 0

These two equations are called secular equations.


The equations are of the form,
ax + by = 0
cx + dy = 0

If we solve this set of linear, homogeneous equations, we get:

(ad – bc) y = 0

For this to be valid, either y has to be zero or the coefficient has to be zero. The non-trivial solution
is the later which can be expressed in the determinental form.

a b
=0
c d

These conditions are the same for secular equations. Then,

H11 – ES11 H12 – ES12


=0
H21 – ES21 H22 – ES22

For a wave function represented as n independent terms,

H11 – ES11 H12 – ES12 … Hln - ESln

H21 – ES21 H22 – ES22 … H2n – ES2n

. . . =0

. . .
Hn1 – ESn1 Hn2 – ESn2 … Hnn – ESnn

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