Theoretical investigations of the time-resolved photodissociation dynamics of IBr(-)

The role of laser pulse width as well as other quantum mechanical effects in the interpretation of the observed time-resolved photoelectron spectra (TRPES) of IBr(-) are investigated using conditions that are chosen to reproduce those used for the experimental study of Mabbs et al. [ J. Chem. Phys. 2005 , 122 , 174305 ]. In that study, it was shown that one could correlate shifts in the frequency of the maximum in signal as a function of time to differences between the potential energies of the electronic states that are accessed by the pump and probe lasers. While this classical picture is attractive, it is based on a single trajectory with an initial I-Br separation that is ∼0.3 Å longer than the equilibrium value. In addition, it does not include the role of the pulse widths and other possible quantum effects. In the present work, the six lowest energy electronic states of IBr(-) were calculated at the MR-SO-CISD/aug-cc-pVDZ level of theory/basis set as a function of the I-Br distance. The TRPES of IBr(-) were calculated in three pulse regimes: an infinitesimally short pulse, an intermediate pulse that has a temporal full width at half-maximum (fwhm) of 300 fs, which was chosen to match the experimental value, and one that is 3 times longer than the experimental value. The resulting spectra are qualitatively different, and the sources of these differences are discussed. The intermediate pulse provides very good agreement with experiment with the introduction of no adjustable parameters. The origins of the features of the experimental signal are discussed in terms of this fully quantum mechanical picture.