2
$\begingroup$

Calculating transition matrix elements can be difficult, and I have found myself needing to use hydrogenic electric dipole transition matrix elements a fair bit.

$$\mathbf{r}_{nlm}^{n'l'm'}=\langle\psi_{nlm}~|~\mathbf{r}~|~\psi_{n'l'm'}\rangle$$

Is there any online source that gives the nontrivial matrix elements above (for hydrogen obviously)?

$\endgroup$
3
  • 1
    $\begingroup$ I never worked my way through Salpeter and Bethe's book on one- and two-electron atoms, but that might may give some pointers. $\endgroup$
    – Jon Custer
    Oct 5, 2016 at 12:34
  • 2
    $\begingroup$ There is a list of spectroscopic databases from the NIST, including a database for many types of atoms that includes many (though not all) transition probabilities. $\endgroup$ Oct 6, 2016 at 4:07
  • $\begingroup$ This answer provides an analytic formula for the radial matrix elements of $r^k$. You can derive your matrix elements from this. $\endgroup$
    – Ghoster
    Jan 30 at 6:01

1 Answer 1

3
$\begingroup$

As a partial answer, I took the advice of @JonCuster and pulled the following equations from "Quantum Mechanics of One- & Two- Electron Atoms" by Bethe and Salpeter. All results are in C.G.S units.

The sum of dipole transition intensities for initial state $(n,l,m)$ and final states $(n',l+1,m')$, where $m'$ runs over the three allowed values ($m'=m-1,m,m+1$), is given by

$$\sum_{m'}|\mathbf{r}_{n,l,m}^{n',l+1,m'}|^2=\frac{l+1}{2l+1}\left(R_{n,l}^{n',l+1}\right)^2$$

Similarly, we have for final states with $l'=l-1$,

$$\sum_{m'}|\mathbf{r}_{n,l,m}^{n',l-1,m'}|^2=\frac{l}{2l+1}\left(R_{n,l}^{n',l-1}\right)^2$$

Here, the symbol $R_{n,l}^{n',l'}$ represents the radial overlap between hydrogenic states $(n,l)$ and $(n',l')$. A consequence of the above equations is that the lifetime of a state does not depend on the magnetic quantum number $m$.

The closed-form expressions for the radial overlap matrix elements in their full generality are highly complicated. Quoted once again from Bethe and Salpeter (who themselves quote W. Gordon), for $n'\neq n$,

$$\begin{align*} R_{nl}^{n',l-1}&=\frac{(-1)^{n'-1}}{4(2l-1)}!\sqrt{\frac{(n+l)!(n'+l-1)!}{(n-l-1)!(n'-1)!}}\frac{(4nn')^{l+1}(n-n')^{n+n'-2l-2}}{(n+n')^{n+n'}}\times\\ &\times\left\{F\left(-n_r,-n_r',2l,-\frac{4nn'}{(n-n')^2}\right)-\left(\frac{n-n'}{n+n'}\right)^2 F\left(-n_r,-2,-n_r',2l,-\frac{4nn'}{(n-n')^2}\right)\right\} \end{align*}$$

where $F(\alpha,\beta,\gamma,x)$ is the hypergeometric function, $n_r=n-l-1$ and $n_r'=n'-l$ are the radial quantum numbers for the two states.

EDIT: I could almost swear that I stumbled upon a random website in which you could type in whatever transition matrix element you wanted and it would spit it out (presumably from a pre-calculated table). It had an enormous amount of dipole and quadrupole transition matrix elements (for sure electric, maybe magnetic?). I really don't think I was dreaming when I came across it, but now I'm not too sure since I can't find it anywhere. I think it may have been associated with the authors of this paper, but I'm not too sure.


[1] "Quantum Mechanics of One- & Two- Electron Atoms" by Bethe and Salpeter

[2] (German) W. Gordon: Ann. d. Pys. (5) 2, 1031 (1929) - radial overlap integrals are calculated here. They are of course expressed in units of the bohr radius.

$\endgroup$
1
  • $\begingroup$ This answer provides an analytic formula for the radial matrix elements of $r^k$. The matrix elements in this question can be derived from this. $\endgroup$
    – Ghoster
    Jan 30 at 6:02

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service and acknowledge that you have read and understand our privacy policy and code of conduct.

Not the answer you're looking for? Browse other questions tagged or ask your own question.