A full-dimensional wave packet dynamics study of the photodetachment spectra of FCH4-

作者：Palma Juliana; Manthe Uwe

来源：Journal of Chemical Physics, 2012, 137(4): 044306.

DOI：10.1063/1.4737382

The low-resolution photodetachment spectrum of FCH4- is studied in full dimensionality employing the multi-configurational time-dependent Hartree approach and potential energy surfaces recently developed by Bowman and co-workers. The computed spectrum qualitatively agrees with the low-resolution spectrum measured by Neumark and co-workers. It displays two peaks which can be assigned to different vibrational states of methane in the quasi-bound F center dot CH4 van der Waals complex. The first intense peak correlates to methane in its vibrational ground state while the second much smaller peak results from methane where one of the bending modes is excited. The present simulations consider only a single potential energy surface for the neutral FCH4 system and thus do not include spectral contributions arising from transitions to excited electronic states correlating to the F(P-2) + CH4 asymptote. Considering the quantitative differences between the computed and the experimental spectra, one cannot decide whether beside the vibrational excitation of the methane fragment also electronic excitation of FCH4 contributes to the second peak in the experimental photodetachment spectrum.

• 出版日期2012-7-28