L18.

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Lecture 18

The variational principle

The variational principle let you get an upper bound for the ground state energy
when you can not directly solve the Schrödinger's equation.

How does it work?

(1) Pick any normalized function .

(2) The ground state energy Egs is

3) Some choices of the trial function will get your Egs that is close
to actual value.

The ground state of Helium

Two electrons orbiting the nucleus with charge Z=2.

(ignoring fine structure and smaller corrections).

Experimental result:

Our task: use variational principle to get as close as possible to experimental result.

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If we ignore term

our problem reduces to two independent Hydrogen-like hamiltonians with Z=2. In this
case, the solution for the ground state is just a product of two hydrogen ground state
wave functions with Z=2.

The energy is just the sum of two hydrogen-like energies with Z=2:

Rather far from experiment value of -79eV.

To get a better approximation, we apply variational principle with trial function (1).

We need to calculate the expectation value

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We calculate integral first, we orient our coordinate system so z is along .

Integral over gives

Integral over is

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Angular integrals give 4π, integral over r1 gives

Much closer to -79 eV!

We can do even better!

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The ground state of Helium: how to improve the result?

Our initial trial function was:

Now, we take

and take Z to be a parameter. We re-write the Hamiltonian as

Note, that we did not change our Hamiltonian (we are not allowed to do that in the
variational method). We just added and subtracted

We now calculate the expectation value

with our "new" trial function

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as before.
Note: if Z=2

We need to calculate

where is the Bohr radius

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We already calculated the third term:

For our new trial function,

Putting it all together, we get

For convenience, let's express all terms via E1:

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Therefore, for any Z

We yet the lowest upper bound when is minimized.

Class exercise: minimize . Find Z and get the lowest upper bound for Egs (i.e. a
number in eV).

Even closer to the experimental value -79.0 eV!

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Summary: variational method

The variational principle let you get an upper bound for the ground state energy
when you can not directly solve the Schrödinger's equation.

How does it work?

(1) Pick any normalized function .

(2) The ground state energy Egs is

3) Some choices of the trial function will get your Egs that is close
to actual value.

If you picked a function with a parameter, minimize the resulting expression for .
Substitute resulting value of the parameter into to get lowest upper bound on Egs.

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