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Methods for Calculating Partition Functions of Molecules Involving Large Amplitude and/or Anharmonic Motions

2016; American Chemical Society; Volume: 12; Issue: 3 Linguagem: Inglês

10.1021/acs.jctc.5b01094

1549-9626

Dimitrios Skouteris, Danilo Calderini, Vincenzo Barone,

Chemical Thermodynamics and Molecular Structure

We present a method for calculating partition functions taking into account anharmonic contributions for systems involving both small-amplitude vibrations and hindered rotations. The Wang-Landau scheme is used in the first case, while two alternative schemes are used for hindered rotation based on imaginary time propagation and fitting of the exact energy levels as a function of quantum number. These two schemes are shown to be complementary in their ranges of applicability (in terms of the torsional rotational constant and the relevant potential). Partition functions for four different molecules are calculated and compared to simpler ones obtained using a harmonic model.