Resonance Raman overtone progressions of I2 in an Ar crystal are computed using the time dependent formula of Raman scattering which has been known to possess distinct computational advantages over the Kramers-Heisenberg- Dirac sum-over-states method, especially when treating condensed phase systems. The symmetrized split operator fast Fourier transform method, which provides a simple and accurate algorithm, is applied to computing the time evolution of the vibrational wave packet involved in the time dependent formula. Our calculated result based on Heller's time dependent formula is in qualitative agreement with the experimental one of Grzybowski and Andrews, but there are some discrepancies between them (for example, the overtone enhancement with the 530.9 nm excitation is not so strong as the experimental one). Those discrepancies are ascribed to the adopted assumption that the line shape for a vibronic transition is a Lorentzian and it is independent of the vibrational level in the excited electronic state. The use of an incident frequency dependent line shape proves to resolve the disagreements to a great extent, which implies that to obtain perfect agreement one needs to explicitly deal with the motion of the trapped molecule and its neighboring host atoms.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry