Analytic energy-level densities of separable harmonic oscillators including approximate hindered rotor corrections

摘要

Energy-level densities are key for obtaining various chemical properties. In chemical kinetics, energy-level densities are used to predict thermochemistry and microscopic reaction rates. Here, an analytic energy-level density formulation is derived using inverse Laplace transformation of harmonic oscillator partition functions. Anharmonic contributions to the energy-level density are considered approximately using a literature model for the transition from harmonic to free motions. The present analytic energy-level density formulation for rigid rotor-harmonic oscillator systems is validated against the well-studied CO + O ˙ H system. The approximate hindered rotor energy-level density corrections are validated against the well-studied H₂O₂ system. The presented analytic energy-level density formulation gives a basis for developing novel numerical simulation schemes for chemical processes.