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Subject PHYSICAL CHEMISTRY

Paper No and Title 2, PHYSICAL CHEMISTRY-II

Module No 14: VARIATION METHOD - APPLICATIONS

Module Tag CHE_P2_M14

TABLE OF CONTENTS
1. Learning Outcomes
2. Application of Variation Method
2.1 Simple case: Particle in a one dimensional box
2.2 Helium atom
3. Summary

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications
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1. Learning Outcomes
After studying this module, you shall be able to

• Write Schrödinger equation for complex systems using the variation method.
• Solve Schrödinger equation for Helium atom using variation method.

2. Application of Variation method

Variation method is an approximate approach used in quantum mechanics. The basic principle of
variation method is to guess a trial wave function for the problem, which consists of some
adjustable parameters called variational parameters. These variational parameters are fixed to
minimize the energy for the chosen trial wave function. The resulting trial wave function and
corresponding energy are variation method approximations to the exact wave function and
energy.
Variation method calculates an upper bound (Ea) to the ground state energy Eo by using any
appropriate guess/ trial function (φa).
^
ϕ a* H ϕ a dτ
Ea =
∫ ≥ Eo
* …..(1)
∫ ϕ ϕ dτ
a a

The most important step for solving eigen value of the complex system using variation method is
choosing or guessing the right guess/trial function φa which determines the success of the
variation method. A trial function can be taken as a linear combination of n linearly independent
functions.

ϕa = ∑a ψ n n , where an are the variational parameters …..(2)

The trial function so chosen must satisfy the same boundary conditions as the exact wave
function and should be normalized.

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications
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In order to elaborate further the significance of variation theorem, we shall derive approximate
energy values for two cases using variation method, (i) a model system of a particle in one
dimensional box and (ii) the chemical system of helium atom for which Schrödinger equation
cannot be solved exactly.

2.1 Simple case: Particle in a one dimensional box

The simplest application of variation method is to solve the case of a particle in a one
dimensional box.

Figure 1: Particle in a one dimensional box

Consider the trial function for the problem as

ϕ a = x( L − x), where x = [0, L] …..(3)

Over here, the trial function so considered contains no variational parameter. But suppose if the
trial wave function would have been
ϕ a = x(kL − x), where x = [0, L] , then coefficient k would have represented the variational
parameter in the equation.

The Hamiltonian for the particle in a one dimensional box is given by

^ h2 d 2 …..(4)
H =− . 2
o
8π 2 m dx
Substituting the trial function as given in equation (3) and Hamiltonian from equation (4) into
equation (1) gives

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications
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− h2 d 2
∫ x ( L − x ){ 2
. 2 }x( L − x)dx
Ea = 8π m dx …..(5)

∫ x( L − x) x( L − x)dx
This on integration gives,

L3
{ }
− h2 6 10 h2 h2 …..(6)
Ea = = 2( ) ≈ 1.014( )
8π 2 m L5 π 8mL2 8mL2
{ }
30
For the problem of particle in a one dimensional box, the ground state energy is given by the
equation,

h2 …..(7)
E0 =
8mL2
On comparing equation (6) with equation (7), we find that

Ea > Eo .....(8)

This shows that the variation method calculates an upper bound (Ea) to the ground state energy Eo
by using an appropriate trial function (φa).

2.2 Helium atom

Helium atom is a three particle system (2 electrons and one nucleus) for which the eigen states
and eigen values cannot be obtained exactly. Therefore, we use here variation method to calculate
approximate ground state energy for the helium atom.

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications
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The helium atom has two electrons with coordinates r1and r2 with respect to nucleus which carries
+2e charge (Z = 2). The Schrödinger equation for helium atom is given as

^ h2 h2 2e 2 2e 2 e2
H =− ∇(2
e1 + ∇ 2
e2 − ) ∇ 2
n − − + …..(9)
8π 2 me 8π 2 mn 4πε 0 r1 4πε 0 r2 4πε 0 r12
where me is the electronic mass, mn is the mass of the nucleus; 𝛻!! is the laplacian operator with
respect to the position of the nucleus and 𝛻!! is the laplacian operator with respect to the
electronic coordinates of the two respective electrons present in the system.

To simplify this 3 particle problem, nucleus is considered fixed at the origin as mn>>me, which
reduces the Schrödinger equation to

…..(10)
^ h2 2e 2 2e 2 e2
H =−
8π 2me
(
∇e21 + ∇e22 − ) 4πε 0r1
−
4πε 0r2
+
4πε 0r12

In atomic units, equation (10) modifies to

^ 1 2 1 2 2 1
H =− ∇ e1 − ∇ e22 − − + …..(11)
2 2 r1 r2 r12

Let the trial function be of the form

Z3
ϕa (r1 , r2 ) = e − Z ( r1 + r2 ) …..(12)
π

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications
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where Z is an adjustable parameter.

For one electron system like hydrogen atom or He1+ , wave function is known to be of the form

Z3 1 − Zr
ao
Ψ=( ) 2
e …..(13)
π
with ao represents the bohr’s radius and Z the charge on the nucleus.

With this equation (11) can be simplified as

…..(14)
^ 1 2 Z 1 2 Z ( Z − 2) ( Z − 2) 1
H =− ∇ e1 − − ∇e2 − − − +
2 r1 2 r2 r1 r2 r12

where one electron part can be written as

…..(15)
3 2 3
1 2 Z Z 12 −Zr Z Z 12 −Zr
(− ∇ − )( ) e =− ( ) e
2 r π 2 π
The approximate energy for this problem is then calculated using

^
E a = ∫ dr1dr2ϕ a H ϕ a …..(16)

where Ĥ is taken from equation (14) and trial function from equation (12)

Substituting the trial function and Hamiltonian in equation (16) gives

Z6 − Z ( r1 + r2 ) 1 Z 1 Z ( Z − 2) ( Z − 2) 1 − Z ( r1 + r2 )
Ea = 2 ∫∫e [− ∇ e21 − − ∇ e22 − − − + ]e dr1dr2
π 2 r1 2 r2 r1 r2 r12
This on integration gives

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications
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27
Ea = Z 2 − Z …..(17)
8

As stated earlier that Z is an adjustable variation parameter. In order to minimize the energy,
equation (17), i.e, energy is differentiated with respect to Z and equated to zero, which gives

27
Z min = ……(18)
16

Helium atom is a 2 electron system while hydrogen is a one electron system. If we ignore the
inter-electron interaction in helium atom, the ground state wave function for helium atom can be
taken as a product of individual electron wave function, i.e., it can be approximated as product of
individual hydrogen like one electron wave function.

Ψo (r1 , r2 ) = ψ 1 (r1 ).ψ 2 (r2 ) …..(19)

Since energy is an additive property, it means on ignoring inter-electron repulsion, Helium atom
energy becomes sum of energy of two hydrogen atoms.
The energy of hydrogen atom is given by

2π 2 me Z 2 e 4
EH =− 2 2
n h ( 4πε o ) 2
with Z = 1.

So, the helium atoms energy becomes

2π 2 me Z 2 e 4 2π 2 me Z 2 e 4
EHe =− 2 2 −
n h (4πε o ) 2 n 2 h 2 (4πε o ) 2
which on simplification in terms of atomic units gives

Z2
EHe = − …..(20)
n2

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications
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with n = 1 for ground state.

Now, substituting the value of Zmin from equation (18) into equation (20) gives
27 2
E He = − Z 2 = −( ) = −2.8477 au = −77.5 eV …..(21)
16

The experimental value of the energy is -2.9033 au (-79.00 eV). Comparing this energy with the

variation approximate energy gives a result with 2% discrepancy. The result indicates that the

variation method provides a fairly good route for solving complex quantum systems.

Note: The variation method is a robust technique in situations where it is hard to determine a

good unperturbed Hamiltonian. While, in cases where there is a good unperturbed Hamiltonian,

perturbation theory can be more efficient than variation method.

For the problem of helium atom, approximate energy obtained from perturbation theory is -74.83

eV while that obtained from variation method is -77.5 eV. Comparing the results with

experimental energy value which is -79.00 eV, we conclude that the variation method gives better

results than perturbation theory for the case of helium atom.

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications
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3 Summary

• Variation method is an approximate approach used in quantum mechanics

• Variation method calculates an upper bound (Ea) to the ground state energy Eo by using
appropriate guess/ trial function (φa)
^
ϕ a* H ϕ a dτ
Ea =
∫ ≥ Eo
*
∫ ϕ ϕ dτ
a a

• The approximate variation energy for helium atom comes out to be -77.5 eV which is in
2% error with respect to the experimental value which is -79.00 eV.
27 2
E He = − Z 2 = −( ) = −2.8477 au = −77.5 eV
16

CHEMISTRY PAPER: 2, PHYSICAL CHEMISTRY-I

MODULE No:14, VARIATION METHOD -Applications