Dipole

matrix elements govern photo-induced transitions The electric field of light couples to the dipole moment of molecules and that is how photons exchange with matter to cause absorption and emission of light. Let be the dipole moment of a molecule in a given electronic state, e.g., the ground electronic state. The magnitude of the vector depends of the internuclear distances and angles. For a diatomic, e.g., HCl, there is just one internulcear distance, R and just one component of i.e., the component along the R-axis which we denote z. It is common to expand in a Taylor series about Re, i.e.,
( R) ( Re ) +
d dR ( R Re ) e + '( Re )( R Re )
R= Re

a) For pure rotational transitions, that is where no change in v occurs, the constant term governs the intensity:

I rot j ' m ' e jm ; e = e cos jm = Y j ,m (, ) j ' m ' e jm e m ',m j ', j 1

Mnemonic: rigid dipole goes with rigid rotor transitions.

b) For vibrational transitions '( Re )( R Re ) governs transitions

I vib ( 'e )2 v ' ( R Re v . For HO I vib ( 'e )2 v ',v1

Combining a) and b), for ro-vib transitions

I vibrot ( 'e )2 v ',v1 j ', j 1 . Selection rules are therefore: v= 1 j=1

These hold for polyatomics as well as diatomics, with some additions for polys in the case of rotational transitions These results are completely consistent with our earlier discussion of the HBr ro-vibrational emission spectrum. Another example is the ro- vibrational absorption spectrum of HBr take from the text and shown below.

HBr ca 298 K

Next we consider electronic spectroscopy

 O2 Potential Curves Recall O2 Bonding from the familiar figure below The important part of the configuration shown, which is indeed the lowest energy one is xy which gives states 3 g , 1 g of which 3 g is the lowest. The other possible configuration is x2 , y2 1 g state, which is lower in energy than 1 g . So there is a Born-Oppenheimer potential for each electronic state (recall H2+). These states are all bonding from the diagram above and they are sketched below along with two other curves.

 Each potential has its own characteristics, i.e., Re, De, and e, and the vibrational energies are schematically indicated in each. The vibrational energies and rotational energies in general are different for each electronic state. For example, Be =
2 . This is not new. What is 2 Re2

new is the possibility of transitions between these electronic states. This does happen and as usual there are selection rules for these. First S = 0 To investigate this further we need to dig deeper into the Born- Oppenheimer approximation.
4

The total Hamiltonian = H el + Tnuclear .

[Tnuclear + Eel ( R)] nuclear (R ) = E nuclear (R )

And so finally the total wavefunction is given by

H el el (r ; R ) = Eel ( R) el (r ; R )

tot = el (r ; R ) nuclear (R )
To be more concrete apply this to O2 in which case

tot = e (r ; R ) v ( R)Y j ,m ( , )
is the electronic wavefunction that determines the potential that governs the nuclear motion. Consider now an electronic transition between two electronic states, which we denote generically as e to e. Again a dipole operator couples these states but now it depends on the electronic degrees of freedom. It also depends on the nuclear ones, but much more weakly, so to a good approximation we consider just the dependence on electronic degrees of freedom. Thus,

I e' (r ; R ) v' (R)Yj',m ' ( , ) (r) e (r ; R ) v (R)Yj,m ( , ) = e' (r ; R ) (r) e (r ; R ) = Ie'e v' (R) v (R) j', j1
The Franck-Condon factor is v ' ( R ) v ( R )
2
2 2

v' (R)Yj',m ' ( , ) cos v (R)Yj,m ( , )