Comparison of algorithms for the calculation of molecular vibrational level densities.
Level densities of vibrational degrees of freedom are calculated numerically with formulas based on the inversion of the canonical vibrational partition function. The calculated level densities are compared with other approximate equations from literature and with the exact Beyer-Swinehart values, for which a simplified but equivalent version is given. All approximate equations agree at high excitation energies, but our results are vastly superior at low energies for large molecules. The results presented here are therefore of particular relevance for thermal processes of very large molecules, e.g., of biological nature, for which the exact state counting can be prohibitively slow. Furthermore, it is valid for situations where anharmonic motion significantly influences the thermal properties.
Hansen
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Department of Physics, University of Gothenburg, SE-412 96 Göteborg, Sweden. klavs@physics.gu.se