Lecture 14:

Selection Rules of (electric-dipole) Quantum Transitions (essentially a tutorial session on angular momentum operators)

Important for understanding spectroscopy

Important for understanding decay rates of atomic levels

Normally the dipole interaction Hamiltonian dominates, and we have

Stimulated emission rate Spontaneous emission rate

where

(for single-electron case, for convenience)

is the transition dipole moment, or the matrix elements of the dipole operator between the two states involved in a transition.

Selection rules will tell us when the transition dipole moment is zero, thus simplifying our calculations

Consider first rotationally symmetric (and spinless) systems

(not necessarily for hydrogen atom)

Eigenstates will be like

radial part spherical harmonics

So the selection rule question becomes:

A quick example:

Because each term in the kernel is an odd function of x, y, or z

Hence, l = 0 l = 0 transitions are not allowed within the dipole approximation.

Selection rules involving m and m

If

then

If

then

Combining the results along directions of x,y, and z:

The dipole transition moment has nonzero components only if

So this saves us from calculating millions of matrix elements

Drifting away a little bit: Alternative proofs

Hence:

Obviously, is nonzero only if m=m. In fact this is true even if z is changed to any function of z.

Also: Obviously, it is nonzero only if |m-m|=1.

Question: What if we also consider spin degrees of freedom ?

Because we still have the following commutation relations when replacing L by J = L+S :

Exactly the same derivations apply to the total angular momentum operator !!

To be completed during the lecture

Selection rules involving the quantum number This time using this commutation relation

(check by yourself)

continued on the next slide

Continuing the previous slide: So if then must be zero.

That is, only if Or equivalently: Or equivalently:

then

can be nonzero.

Question: Will the selection rule

survive if we include spin degrees of freedom?

That is: can still be determined by ?

Simple answer: Yes, because states

of

are still eigenstates

, so the above derivations still apply if we use

eigenstates of the total angular momentum operators. Additional note: If expressed in j, we need to have j= 0, 1, or -1 for nonzero dipole transitions (by Wigner-Eckhart theorem).

Spontaneous emission route in the case of hydrogen atom

l =0 n=4 n=3 n=2

Metastable

l=1

l=2

l=3

n=1
color is not associated with transition frequencies, here only used to denote changes in n

Comments:
Using only commutation relations between angular momentum operators and position operators, selection rules for dipole transitions can be derived.

When electric dipole transitions are not allowed, the quantum transitions are still possible due to other small effects, such as collisions or quadrupole interactions or magnetic dipole interactions. But these transitions are often much slower than dipole allowed transitions.