Accurate evaluation of internal energy level sums and densities including anharmonic oscillators and hindered rotors

Abstract

The calculation of molecular energy level sums and densities is necessary for the treatment of many physical and chemical problems including reaction rates. An extension of Beyer and Swinehart's algorithm for directly computing harmonic oscillator eigenstate sums and densities is described. With this new algorithm it is possible to compute exact or near-exact energy level sums and densities for degrees of freedom such as free and hindered rotors and anharmonic oscillators so long as the energy levels for each degree of freedom can be specified. Computer calculation by this technique is practical even for large molecules up to all chemically interesting energies and error is confined to small rounding errors. Results by this algorithm are compared to values of energy level sums that have been given in the literature by various alternative approximate treatments and permit more rigorous testing of the latter and assessment of the approximations involved.