Statistical phase space theory of polyatomic systems: Rigorous energy and angular momentum conservation in reactions involving symmetric polyatomic species
Abstract
Classical formulas for the sum and density of rotational and rotationalorbital states pairs of polyatomic molecules are derived using a geometrical approach that rigorously conserves energy and angular momentum. The pair combinations considered include a spherical top in combination with either a linear, spherical, or symmetric top molecule. With the formulas presented here it is possible to perform exact classical statistical phase space theory calculations for bimolecular reactions involving polyatomic molecules. In suitable limits our results reduce to wellknown classical expressions for rotational state densities and sums or to equations previously derived by Klots using an aprroximate phase space approach. Calculations are given that demonstrate the distortions produced in the system phase space by molecular oblateness and prolateness are usually small.
 Publication:

Journal of Chemical Physics
 Pub Date:
 March 1977
 DOI:
 10.1063/1.434292
 Bibcode:
 1977JChPh..66.2306C
 Keywords:

 Angular Momentum;
 Chemical Reactions;
 Energy Conservation;
 Molecular Collisions;
 Molecular Rotation;
 Polyatomic Molecules;
 Molecular Oscillations;
 Partitions (Mathematics);
 Physical Chemistry;
 Atomic and Molecular Physics;
 82.20.Db;
 Transition state theory and statistical theories of rate constants