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

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.

[1]  W. Forst.  Methods for calculating energy-level densities , 1971 .

[2]  J. C. Tou,et al.  Computation of Statistical Complexions by the Method of Steepest Descent , 1968 .

[3]  G. Whitten,et al.  Vibration‐Rotation Energy‐Level Density Calculations , 1968 .

[4]  H. Eyring,et al.  Calculation of Statistical Complexions of Harmonic Oscillations , 1965 .

[5]  G. Whitten,et al.  Approximation for Rotation—Vibration Energy Level Sums , 1964 .

[6]  E. W. Schlag,et al.  Computation of Statistical Complexions. II. Effect of Anharmonic Level Spacings , 1964 .

[7]  E. Thiele.  Smooth Curve Approximation to the Energy-Level Distribution for Quantum Harmonic Oscillators , 1963 .

[8]  J. H. Current,et al.  Decomposition of Chemically Activated Ethyl‐d3 Radicals. Primary Intramolecular Kinetic Isotope Effect in a Nonequilibrium System , 1963 .

[9]  F. W. Schneider,et al.  The Thermal Unimolecular Isomerization of Methyl Isocyanide. Fall-of Behaviour , 1962 .

[10]  E. W. Schlag,et al.  Computation of Statistical Complexions as Applied to Unimolecular Reactions , 1962 .

[11]  J. H. Current,et al.  On the Classical Approximation in Unimolecular Reactions and Mass Spectra , 1961 .

[12]  J. Magee,et al.  Comparison of Hot and Thermal Reactions , 1959 .

[13]  R. Marcus.  Unimolecular dissociations and free radical recombination reactions , 1952 .

[14]  J. Koehler,et al.  Hindered Rotation in Methyl Alcohol , 1940 .

[15]  S. Bauer.  Inversion of the Partition Function to Determine the Density of Energy States , 1939 .

[16]  M. Hoare,et al.  Densities of states and the complex partition function , 1971 .

[17]  M. Hoare,et al.  Inversion of the Partition Function: The First‐Order Steepest‐Descent Method , 1970 .

[18]  P. Haarhoff.  The density of vibrational energy levels of polyatomic molecules , 1964 .