I may be wrong here as this was long ago, but if I remember correctly absorption of light and the excitation process of an electron (for example) are faster than the electronic movement and therefor appear as a straight vertical line on the energy to distance plot (Jablonski-diagram). So you start from an optimized geometry for the ground state which is not necessarily the optimized geometry for the excited that and it will relax in the time while it is being excited before it falls back to the ground state. I remember we used this electronic change to calculate pKs values of acids for example. So yes, if I remember correctly the x-axis on this diagram was the distance of the electron to the nucleus (but I could be wrong there).
There was a rule for the excitation process, I think by Fermi (?). Historically seen, when they first analyzed the emission spectrum of for example hydrogen, they found that not every possible transition is equally likely, so there has to be quantum-mechanical process which descides what transition is more likely. And as the excitation process is much faster it needs to be almost straight up, so without any change in the geometry or any distances. And essentially you will need a good overlap of those amplitudes.
If you look here for example:
You can see that both of these curves represent the different vibrational states and those have amplitudes, which tend to be bigger and the sides and not in the middle. I think in classical mechanics you'd expect that to be somewhere around the point where the oscillating spring is relaxed. And you can show, that the absorption process is better if the overlap of those amplitudes is at it's biggest, so you start from the ground state and then you go straight upwards till you find a higher vibrational mode of the excited state where you end up in a high amplitude. This is why you end up in v'=2 in the picture. Then you still have the same geometry but it is a vibrationally exicted state and will first relax to the excited vibrational ground state v'= 0. But that curve is shifted to the right and this is how the geometry changes and I believe in you example this would be the orientation of the electron to the nucleus.
At least I hope so. If not I'm truly sorry but this was the only example I came up with right now.