Quantum Mechanics – How First Order Energy Correction Formula Works in Non-Degenerate Perturbation Theory

perturbation-theoryquantum mechanics

I'm studying for a test in quantum mechanics and I'm currently trying to learn about perturbation theory and I've realized that I don't quite understand what I'm doing when I'm doing my calculations.

Considering the case of non-degenerate perturbation theory, the formula for the first order energy correction is

$$E_n^1=\langle \psi_n^0|H'|\psi_n^0 \rangle.$$

  • What exactly does this mean?
  • I understand that it's some kind of expectation value of the perturbation but what more? And what is the meaning of $n$?

Best Answer

What you do in perturbation theory is you assume the correct eigenvalue equation for a (hitherto) unknown correct wavefuction $|\psi_n\rangle$ and its associated eigenvalue $E_n$: $$ H|\psi_n\rangle = E_n |\psi_n\rangle,$$ where $H$ is the full Hamiltionian.

What you have is a main contribution $H_0$ (e.g. the Coulomb potential) and a perturbation $H'$ which is small compared to $H_0$ and that will therefore just slightly change the main solution.

You then assume that you can expand the correct solution for the energy and the wavefunction as a perturbative series, i.e. in terms that are smaller and smaller: $$ |\psi_n\rangle = |\psi_n\rangle^0 + |\psi_n\rangle^1 + |\psi_n\rangle^2 ...$$ $$ E_n = E_n^0 + E_n^1 + E_n^2 ... $$ where the exponents signify the order of the term. Higher order terms are smaller, and therefore only needed in you want higher precision.

Now, the full TISE becomes: $$ (H_0 + H')\,(|\psi_n\rangle^0 + |\psi_n\rangle^1 + |\psi_n\rangle^2 ... ) = (E_n^0 + E_n^1 + E_n^2 + ...)\,(|\psi_n\rangle^0 + |\psi_n\rangle^1 + |\psi_n\rangle^2+...)$$

Now you take the $0^{th}$ order equation -- where each term is of $O^{th}$ order:

$$H_0 |\psi_n\rangle^0\rangle = E_n^0 |\psi_n\rangle^0,$$ which is just the unperturbed equation, and therefore the starting point for any perturbative calculation.

Now look at the $1^{st}$ order equation -- remember that two $1^{st}$ order terms multiplied together give you a $2^{nd}$ order terms, whereas you only want to keep the $1^{st}$ order ones. $H'$ is first order:

$$ H_0 |\psi_n\rangle^1 + H'|\psi_n\rangle^0 = E_n^0|\psi_n\rangle^1 + E_n^1 |\psi_n\rangle^0.$$

What you are after is $E_n^1$, i.e. the $1^{st}$ order contribution to the energy.

Multiply by $^0\langle \psi_n|$ from the left:

$$ ^0\langle \psi_n|H_0 |\psi_n\rangle^1 + ^0\langle \psi_n|H'|\psi_n\rangle^0 = ^0\langle \psi_n|E_n^0|\psi_n\rangle^1 + ^0\langle \psi_n|E_n^1 |\psi_n\rangle^0,$$

$$E_n^0 \,^0\langle \psi_n|\psi_n\rangle^1 + \, ^0\langle \psi_n|H'|\psi_n\rangle^0 = E_n^0\,^0\langle \psi_n|\psi_n\rangle^1 + E_n^1 \,^0\langle \psi_n|\psi_n\rangle^0,$$

$$ \implies (E_n^0 - E_n^0) \,^0\langle \psi_n|\psi_n\rangle^1 + ^0\langle \psi_n|H'|\psi_n\rangle^0 = E_n^1 \,^0\langle \psi_n|\psi_n\rangle^0.$$

Assuming normalised states, $^0\langle \psi_n|\psi_n\rangle^0 = 1$, so: $$ E_n^1 = ^0\langle \psi_n|H'|\psi_n\rangle^0 $$.

As other have noted, there's a mistake in you formula.

The same procedure applies for higher order corrections.

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