The molecular origins of the two-dimensional Raman spectrum of an atomic liquid. I. Molecular dynamics simulation

摘要: As complex as it may seem, a two-dimensional (fifth-order) nonresonant Raman spectrum provide one of the simplest ways to get at character intermolecular dynamics in liquids. Its status an echo spectroscopy means that should not only permit us survey vibrations, allow ascertain extent their coherence. Arriving microscopic interpretation those spectra, however, poses some genuine theoretical challenges. We describe here first complete molecular simulation such spectrum. By using classical and focusing on liquid Xe, we find are able produce strikingly similar experimentally reported (nonmagic-angle) spectra CS2. observe, particular, there is no discernable echo, suggesting strongly homogeneously broadened. turn, companion paper, implications these results for instantaneousnormal-mode models