Lecture 8/Tutorial: Variational Principle in Atomic Physics

The ground state of Helium: Having one more electron makes exact solutions impossible. what an embarrassment for physicists !

Of course, this is not at all the biggest embarrassment of physicists:

It's an embarrassment to physicists to have such a conflict between such well verified and accepted theories (Quantum Electrodynamics and General Relativity). In fact it is so painful, that most physicists don't even want to think about it." - Prof. Jordan Maclay

Hamiltonian for the Helium atom:

r1 - r2
-e

-e

r1

r2
+2e

More precisely, mass here should be reduced mass, but that difference is too small compared with the accuracy achievable in a variational principle calculation here. For the same reason, all spins and hence fine/hyperfine structure are neglected

To start with, try 1st order perturbation theory first:

(which is also a variational-principle calculation)

Regarding the electron-electron repulsion as perturbation and then split the Hamiltonian into two parts:

Two non-interacting hydrogenic atoms with Z = 2.

Coulomb repulsion as a perturbation

Ground state of hydrogenic atoms

Hydrogen atom:

Hydrogenic atoms:

energy

state

Unperturbed ground state wavefunction: Product of two hydrogenic ground states with Z=2:

Expectation value of the perturbation:

The predicted ground state is then -8*13.6+ 34 ~ -75 eV

About the integral from the last slide

r 2 - r1 r1

r2
Integrate over r2 first using the following:

continued on the next slide

Continuing the previous slide:

Let Then

The previous integral reduces to

After doing the integral over

The six-dimensional integral can then be reduced as the following:

This integral is trivial (or not?) because each term involves at most an exponential function and a quadratic term

Variational calculations based on physical intuition:

Due to the screening of the other electron, each electron feels a hydrogenic potential with an effective nucleus charge Z (which will be varied when we search for the energy bottom)

To evaluate the expectation value of H on this trial state, rewrite it as

Z-hydrogenic part

Evaluating the expectation value

(think about the hydrogen case Z=1)

(can be directly guessed from early 1st order perturbation calculation for Z=2)

Searching for the bottom:

Compared with the 1st order perturbation theory, much closer to the the experimental value: -79 eV.

Summary:

Assisted with physical insights and intuitions, variational principle may offer a much simpler and better method than perturbation theory Taking advantage of the exact ground states of hygrogenic atoms, we did a variational calculation of the ground state of Helium with an accuracy of 2%. What we learned from the variational calculations is the following: effectively speaking, each electron can only see a nucleus of charge 1.7 or so (due to the screening effect of the other electron).