Comparison of classical, new corrected-classical, and semiclassical IR spectra of non-rotating H2O with quantum calculations

摘要

Model infrared spectra for non-rotating H2O are calculated at 0 K, based on exact quantum, standard classical and semiclassical calculations. An accurate potential energy surface is used along with a realistic dipole function. An analysis of the classical and quantum spectrum in the harmonic approximation is presented at 0 K. This clearly reveals that the magnitude of the classical intensities is essentially arbitrary, depending on the total energy. Thus, the intensity of classical harmonic spectrum disagrees with the corresponding quantum one. A very simple correction to the classical spectrum is suggested that largely restores agreement with the harmonic quantum spectrum. A second, more general classical correction is also suggested, which, however, requires knowledge of the normal modes. (C) 2003 Published by Elsevier B.V. [References: 22]