An example The Na2 double minimum state

As an example we present the results of time-resolved photoelectron spectra of the wavepacket dynamics on the (2) S+ double minimum state of the Na2 molecule computed as outlined in the previous subsections. 

To obtain the photoionization amplitudes, we used our Cl wavefunction for the double-minimum state and a frozen-core Hartree-Fock (FCHF) description of the wavefunction for the ionized state. For the FCHF model the wavefunction is taken to be an antisymmetrized product of HF ion orbitals and a photoelectron orbital that is a solution of a one-electron Schrodinger equation containing the Hartree-Fock potential of the ion core. The HF wavefunction provides a very adequate description of Na over all internu-clear distances of interest. 

The Ci coefficients of Eq. (3.59) incorporate the underlying dynamics into our formulation of time-resolved photoelectron spectroscopy. These 

We have used the formulation, potential curves (see Fig. 3.5), and photoionization matrix elements outlined in the previous sections to study the pump-probe photoelectron spectra in Na2. Important parameters in these studies include. 

Chemical Theory Beyond the Born-Oppenheimer Paradigm 

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