The Variational Theorem

The variational theorem
The variation method allows us to obtain an approximation

to the ground state energy of the system without solving
the Schrödinger equation.
The variation method is based on the following theorem:
Given a system with hamiltonian operator H, then if φ is

any normalized well-behaved function that satisfies the
boundary conditions it is true that
where E0 is the true value of the lowest energy eigenvalue

of H. This important theorem allows us to calculate an
upper bound for the ground state energy.
Practical significance
The variation method serves as the basis for all methods
that use combinations of hydrogen-like orbitals to solve for
the eigenfunctions (wave functions) and eigenvalues (energies)
of atoms and molecules.
The radial part of the hydrogen-like wave functions is modified

by a variational parameter, which is minimized. The theorem
allows us to set the derivative with respect to any parameter α
equal to zero to find the value of that parameter that minimizes
the energy:
We can be sure that the energy calculated in this way will be

greater than the true energy (an upper bound).
The hamiltonian for H
The electronic hamiltonian for the hydrogen atom consists of a
kinetic energy term for the electron and the Coulomb attraction
of the electron and proton (nucleus).
2
– h ∇2
- 2m
+
2
Ze
– r
1
Of course, the nuclear charge of hydrogen is Z = 1 so the
Z is included for completeness. We know that the solutions
Of the Schrödinger equation (HΨ = EΨ) gives energy levels:
2 n is the principal quantum number.
En = – e 12 a0 is the Bohr radius.
2a 0 n
The hamiltonian for He
For helium the same kinetic energy and Coulomb attraction
terms are present, but there is also a Coulomb repulsion
between the two electrons that must be included.
2 e2
– h ∇12
-
r 12 2
2m – h ∇22
- 2m
2
Ze
– r ++
2
1 Ze
– r
2
Because of the Coulomb repulsion there is no exact solution

for He. To solve the problem we use two 1s orbitals from the
solution for hydrogen and then apply the variational method.
The He wave function
The hydrogen 1s wave functions for electrons 1 and 2 are:
The aufbau approach for atoms assumes that the total wave
function for a many-electron atom is just a product of one
electron wave functions. In the present case:
Note that the hydrogen wave functions are normalized so:
�𝑓𝑓1∗ 𝑓𝑓1 𝑑𝑑𝑑𝑑 = �𝑓𝑓2∗ 𝑓𝑓2 𝑑𝑑𝑑𝑑 = 1

Variational approach for the He atom
The He wave function used for the variation method is a
product of two hydrogen 1s orbitals. However, instead of
the nuclear charge Z we use a variational parameter ζ.
3
1 ζ
𝜙𝜙 = 𝑒𝑒 −ζ𝑟𝑟1 ⁄𝑎𝑎 𝑒𝑒 −ζ𝑟𝑟2 ⁄𝑎𝑎
𝜋𝜋 𝑎𝑎
ζ has a physical interpretation. Since one electron tends to
screen the other from the nucleus, each electron is subject to
a nuclear charge that is less than Z.
The hamiltonian is:
ℏ2 2 ζe2 ℏ2 2 ζe2 e2 e2 e2
𝐻𝐻 = − 𝛻𝛻1 − − 𝛻𝛻2 − + ζ−Z + ζ−Z +
2𝑚𝑚 r1 2𝑚𝑚 r2 r1 r2 r12
Evaluation of the integrals
If we consider only the part of the hamiltonian in parentheses
We have the solution to a hydrogen atom with two electrons
in the 1s orbital.
ℏ2 2 ζe2 ℏ2 2 ζe2 ζ2 𝑒𝑒 2
− 𝛻𝛻1 − − 𝛻𝛻2 − 𝜙𝜙 = − 𝜙𝜙
2𝑚𝑚 r1 2𝑚𝑚 r2 𝑎𝑎
where the right hand side is twice the energy of a 1s electron.

The energy can be calculated:
ζ2 𝑒𝑒 2
: � 𝜙𝜙 ∗ 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 = − � 𝜙𝜙 ∗ 𝜙𝜙𝜙𝜙𝜙𝜙
𝑎𝑎
𝜙𝜙 ∗ 𝜙𝜙 𝜙𝜙 ∗ 𝜙𝜙 𝜙𝜙 ∗ 𝜙𝜙
+𝑒𝑒 2 𝜁𝜁 − 𝑍𝑍 � 𝑑𝑑𝑑𝑑 + � 𝑑𝑑𝑑𝑑 + 𝑒𝑒 2 � 𝑑𝑑𝑑𝑑
𝑟𝑟1 𝑟𝑟2 𝑟𝑟12
Evaluation of the integrals
We can evaluate each of the integrals as follows:
𝜙𝜙 ∗ 𝜙𝜙 𝜙𝜙 ∗ 𝜙𝜙 𝜁𝜁
� 𝑑𝑑𝑑𝑑 = � 𝑑𝑑𝑑𝑑 =
𝑟𝑟1 𝑟𝑟2 𝑎𝑎
𝜙𝜙 ∗ 𝜙𝜙 5𝜁𝜁𝑒𝑒 2
� 𝑑𝑑𝑑𝑑 =
𝑟𝑟12 8𝑎𝑎
Evaluation of the variational parameter ζ
We have:
5𝜁𝜁 𝑒𝑒 2
�𝜙𝜙 ∗ 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 = ζ2 − 2𝜁𝜁𝜁𝜁 +
8 𝑎𝑎
We now vary ζ to minimize the variational integral:
𝜕𝜕 𝜕𝜕 5𝜁𝜁 𝑒𝑒 2
� 𝜙𝜙 ∗ 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 = ζ2 − 2𝜁𝜁𝜁𝜁 + =0
𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕 8 𝑎𝑎
𝜕𝜕 2 5𝜁𝜁
ζ − 2𝜁𝜁𝜁𝜁 + =0
𝜕𝜕𝜕𝜕 8
5
2𝜁𝜁 − 2𝑍𝑍 + = 0
8
5
𝜁𝜁 = 𝑍𝑍 −
16
The variational energy:
comparison with experiment
The variational energy is
2 2
∗ 2
5 25 𝑒𝑒 5 𝑒𝑒 2
�𝜙𝜙 𝐻𝐻𝐻𝐻𝐻𝐻𝐻𝐻 = −Z + 𝑍𝑍 − = − 𝑍𝑍 −
8 256 𝑎𝑎 16 𝑎𝑎
Our first guess would be to calculate the energy of the 1s
Electron in He using the hydrogen energy level with a nuclear
charge Z = 2, E = -Ze2/a0 which gives - 2(13.6) eV = -27.2 eV.
Using the value obtained by the variational method we have,
E = -(27/16)e2/a0 = -(27/16)(13.6) eV = -22.95 eV.
The experimental value is -24.5 eV. The variational energy

is much closer to the true value and in accord with
the variational theorem, the true ground state energy is less
than that given by variational method.
Summary for the variational
principle
The hydrogen atom is the only atom with an exact solution.
Hydrogen wave functions are used as the approximation

for atomic wave functions in multielectron atoms.
The variational principle states that any wave function we

choose that satisfies the Schrödinger equation will give
an energy greater than the true energy of the system.
The variation method provides a general prescription for

improving on any wave function with a parameter by
minimizing that function with respect to the parameter.

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The Variational Theorem

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The variational theorem

The variation method allows us to obtain an approximation

Given a system with hamiltonian operator H, then if φ is

where E0 is the true value of the lowest energy eigenvalue

The radial part of the hydrogen-like wave functions is modified

We can be sure that the energy calculated in this way will be

Because of the Coulomb repulsion there is no exact solution

Note that the hydrogen wave functions are normalized so:

�𝑓𝑓1∗ 𝑓𝑓1 𝑑𝑑𝑑𝑑 = �𝑓𝑓2∗ 𝑓𝑓2 𝑑𝑑𝑑𝑑 = 1

where the right hand side is twice the energy of a 1s electron.

The experimental value is -24.5 eV. The variational energy

Hydrogen wave functions are used as the approximation

The variational principle states that any wave function we

The variation method provides a general prescription for

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