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Symmetry numbers for rigid, flexible, and fluxional molecules: theory and applications.

Authors :
Gilson MK
Irikura KK
Source :
The journal of physical chemistry. B [J Phys Chem B] 2010 Dec 16; Vol. 114 (49), pp. 16304-17.
Publication Year :
2010

Abstract

The use of molecular simulations and ab initio calculations to predict thermodynamic properties of molecules has become routine. Such methods rely upon an accurate representation of the molecular partition function or configurational integral, which in turn often includes a rotational symmetry number. However, the reason for including the symmetry number is unclear to many practitioners, and there is also a need for a general prescription for evaluating the symmetry numbers of flexible molecules, i.e., for molecules with thermally active internal degrees of freedom, such as internal rotors. Surprisingly, we have been unable to find any complete and convincing explanations of these important issues in textbooks or the journal literature. The present paper aims to explain why symmetry numbers are needed and how their values should be determined. Both classical and quantum approaches are provided.

Details

Language :
English
ISSN :
1520-5207
Volume :
114
Issue :
49
Database :
MEDLINE
Journal :
The journal of physical chemistry. B
Publication Type :
Academic Journal
Accession number :
21141931
Full Text :
https://doi.org/10.1021/jp110434s