title: Symmetry numbers for rigid, flexible, and fluxional molecules: theory and applications.
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.
authors.affiliation: Skaggs School of Pharmacy and Pharmaceutical Sciences, U.C. San Diego, 9500 Gilman Drive, La Jolla, California 92093-0736, United States. mgilson@ucsd.edu
authors.forename: Michael K
authors.initials: MK
authors.lastname: Gilson
authors.forename: Karl K
authors.initials: KK
authors.lastname: Irikura
mesh_terms: D001554:Benzene / Q000737:chemistry; D008958:Models, Molecular; D056004:Molecular Dynamics Simulation; D013816:Thermodynamics; D047392:beta-Cyclodextrins / Q000737:chemistry
chemical_list: D047392:beta-Cyclodextrins; D001554:Benzene