Statistical thermodynamics of bond torsional modes: tests of separable, almost-separable, and improved Pitzer-Gwinn approximations

• Published in: The Journal of chemical physics Vol. 125; no. 8; p. 084305
• Main Authors: Ellingson, Benjamin A, Lynch, Vanessa Audette, Mielke, Steven L, Truhlar, Donald G
• Format: Journal Article
• Language: English
• Published: United States 28.08.2006
• ISSN: 0021-9606
• DOI: 10.1063/1.2219441

Practical approximation schemes for calculating partition functions of torsional modes are tested against accurate quantum mechanical results for H(2)O(2) and six isotopically substituted hydrogen peroxides. The schemes are classified on the basis of the type and amount of information that is required. First, approximate one-dimensional hindered-rotator partition functions are benchmarked against exact one-dimensional torsion results obtained by eigenvalue summation. The approximate one-dimensional methods tested in this stage include schemes that only require the equilibrium geometries and frequencies, schemes that also require the barrier heights of internal rotation, and schemes that require the whole one-dimensional torsional potential. Then, three classes of approximate full-dimensional vibrational-rotational partition functions are calculated and are compared with the accurate full-dimensional path integral partition functions. These three classes are (1) separable approximations combining harmonic oscillator-rigid rotator models with the one-dimensional torsion schemes, (2) almost-separable approximations in which the nonseparable zero-point energy is used to correct the separable approximations, and (3) improved nonseparable Pitzer-Gwinn-type methods in which approaches of type 1 are used as reference methods in the Pitzer-Gwinn approach. The effectiveness of these methods for the calculation of isotope effects is also studied. Based on the results of these studies, the best schemes of each type are recommended for further use on systems where a corresponding amount of information is available.