Selection rule for electric dipole transitions in x direction

In summary, the integration is correct and it follows that it is only non-zero if m=m'±1. This is because when m=m'±1, one of the exponential terms will become 1 and the resulting non-trigonometric term will become zero when evaluated at 0 and 2π. However, when m≠m'±1, both exponential terms will not become 1 and the resulting non-trigonometric terms will not become zero when evaluated at 0 and 2π.
  • #1
maximus123
50
0
Hello,
I have this matrix element

[itex]\langle n', l', m'| x |n, l, m \rangle[/itex]

where [itex]x=rsin\theta cos\phi[/itex] in spherical polars

Which I write explicitly as:

[itex]=\int \int \int R_{n', l'} R_{n, l} A_{l', m'} A_{l, m} P^{m'}_{l'} P^{m}_{l} e^{im\phi} e^{-im\phi} rsin\theta cos\phi r^{2} sin \theta d \theta d \phi dr[/itex][itex]=A_{l', m'} A_{l, m} \int dr R_{n', l'} r^{3} R_{n, l} \bullet \int d \theta sin^{2} \theta P^{m'}_{l'} P^{m}_{l} \bullet \int^{2\pi}_{0} e^{i\phi(m-m')} cos \phi d \phi[/itex]

The question just wants me to do the integral for the [itex]d \phi[/itex] bit then show that it is only non zero for [itex]m=m' \pm 1[/itex] hence [itex](m-m')= \pm 1[/itex]

So I let [itex]i(m-m')=a[/itex]

[itex]I=\int^{2\pi}_{0} e^{a\phi} cos \phi[/itex]

[itex]u=e^{a\phi}[/itex]
[itex]du=a e^{a\phi}[/itex]
[itex]dv=cos \phi[/itex]
[itex]v=sin \phi[/itex]

[itex]I=sin \phi e^{a\phi}-a \int^{2\pi}_{0} sin \phi e^{a\phi}[/itex]

for the integral here I do the same again

[itex]u=e^{a\phi}[/itex]
[itex]du=a e^{a\phi}[/itex]
[itex]dv=sin \phi[/itex]
[itex]v=-cos \phi[/itex]

[itex]I_{2}=-cos \phi e^{a\phi} +a \int^{2\pi}_{0} cos \phi e^{a\phi}[/itex]

So in total

[itex]\int^{2\pi}_{0} e^{a\phi} cos \phi=sin \phi e^{a\phi}+acos \phi e^{a\phi}-a^{2}\int^{2\pi}_{0} e^{a\phi} cos\phi[/itex]

Then I take the integral on the RHS over to the left, factor out the integral and divide through by [itex]1+a^{2}[/itex] giving:

[itex]\int^{2\pi}_{0} e^{a\phi}cos \phi=\frac{sin\phi e^{a\phi}+acos\phi e^{a\phi}}{1+a^{2}}[/itex]

[itex]= [\frac{sin\phi e^{i(m-m')\phi}+i(m-m')cos\phi e^{i(m-m')\phi}}{1-(m-m')^{2}}]^{2\pi}_{0}[/itex]
Is this integration ok? I kind of made it up as I went along as I wasn't sure how to integrate this function.
Assuming it is could someone explain to me how it follows that it is only non zero if [itex]m=m' \pm 1[/itex]
 
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  • #2
maximus123 said:
[itex]\int^{2\pi}_{0} e^{a\phi}cos \phi=\frac{sin\phi e^{a\phi}+acos\phi e^{a\phi}}{1+a^{2}}[/itex]

[itex]= [\frac{sin\phi e^{i(m-m')\phi}+acos\phi e^{i(m-m')\phi}}{1+(m-m')^{2}}]^{2\pi}_{0}[/itex]

Is this integration ok?

OK, except when you substituted for ##a## in the denominator in the last step.
 
  • #3
Thanks, I've fixed that in the original post
 
  • #4
So, what do you get when m ≠ m' ±1 and what do you get when m = m' ±1?
 
  • #5
I'm having trouble getting passed the fact that for [itex]m=m'\pm 1[/itex] the denominator will be zero
e.g for [itex]m=m'+1[/itex]

[itex]= [\frac{sin\phi e^{i\phi}+icos\phi e^{i\phi}}{1-1}]^{2\pi}_{0}[/itex]
 
  • #6
maximus123 said:
I'm having trouble getting passed the fact that for [itex]m=m'\pm 1[/itex] the denominator will be zero

Right. For this case you will need to go back and substitute [itex]m=m'\pm 1[/itex] before evaluating the integral.
 
  • #7
OK, I think I get this now, so for example for [itex](m-m')=+1[/itex]

[itex]\int^{2\pi}_{0} e^{i(m-m')\phi}cos\phi=\int^{2\pi}_{0} e^{i \phi}cos\phi[/itex]

[itex]=\int^{2\pi}_{0} e^{i \phi} \frac{e^{i\phi}+e^{-i\phi}}{2}[/itex]

[itex]=\frac{1}{2}\int^{2\pi}_{0}e^{2i\phi}+1[/itex]

[itex]=\frac{1}{2}[\frac{e^{2i\phi}}{2i}+\phi]^{2\pi}_{0}[/itex]

[itex]=\frac{1}{2}[\frac{cos(2\phi)+isin(2\phi)}{2i}+\phi]^{2\pi}_{0}[/itex]

[itex]=\frac{1}{2}[\frac{1}{2i}+2\pi-\frac{1}{2i}-0][/itex]

[itex]=\pi[/itex]

Similarly for the case when [itex](m-m')=-1[/itex]

[itex]\int^{2\pi}_{0} e^{i(m-m')\phi}cos\phi=\int^{2\pi}_{0} e^{-i \phi}cos\phi[/itex]

[itex]=\int^{2\pi}_{0} e^{-i \phi} \frac{e^{i\phi}+e^{-i\phi}}{2}[/itex]

[itex]=\frac{1}{2}\int^{2\pi}_{0}e^{-2i\phi}+1[/itex]

[itex]=\frac{1}{2}[-\frac{e^{-2i\phi}}{2i}+\phi]^{2\pi}_{0}[/itex]

[itex]=\frac{1}{2}[\phi -\frac{cos(2\phi)-isin(2\phi)}{2i}]^{2\pi}_{0}[/itex]

[itex]=\frac{1}{2}[2\pi-\frac{1}{2i}+\frac{1}{2i}][/itex]

[itex]=\pi[/itex]

When [itex]m=m'\pm 1[/itex] one of the exponential terms multiplies with another to make 1. This means after integration there is a non trigonometric term which will become zero when zero is substituted into it. However when [itex]m\neq m'\pm 1[/itex] both terms have an exponential in after the integral is evaluated so the two terms you get after subbing in the [itex]2\pi[/itex] will equal the two terms you get after subbing in the zero. Does that sound right? Thanks for the help.
 
  • #8
Sounds good.
 

What is a selection rule for electric dipole transitions in the x direction?

The selection rule for electric dipole transitions in the x direction states that a change in the electronic state of an atom or molecule can only occur when the dipole moment in the x direction changes. This means that the electric dipole moment must have a component in the x direction for a transition to occur.

Why is the selection rule for electric dipole transitions important?

The selection rule for electric dipole transitions is important because it helps us understand and predict which transitions are allowed and which are forbidden in atoms and molecules. This is crucial in the study of spectroscopy, which relies on the analysis of transitions in the electronic states of atoms and molecules.

What are the implications of violating the selection rule for electric dipole transitions in the x direction?

If the selection rule for electric dipole transitions in the x direction is violated, it means that the dipole moment in the x direction has not changed, and therefore the transition is not allowed. This can result in a weak or no signal in spectroscopic measurements, making it difficult to study the electronic states of the atom or molecule.

Are there any exceptions to the selection rule for electric dipole transitions in the x direction?

Yes, there are some exceptions to the selection rule for electric dipole transitions in the x direction. For example, in highly symmetric molecules, such as benzene, the selection rule is relaxed due to the degeneracy of energy levels. Additionally, in certain cases, transitions may be allowed if higher-order effects, such as magnetic dipole transitions, are taken into account.

How does the selection rule for electric dipole transitions in the x direction differ from other selection rules?

The selection rule for electric dipole transitions in the x direction is specific to the direction of the dipole moment. Other selection rules, such as the Laporte selection rule, govern the allowed transitions based on the symmetry of the electronic states. The selection rule for electric dipole transitions in the x direction is also more restrictive, as it only applies to changes in the x direction of the dipole moment, while other selection rules may allow transitions in multiple directions.

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