Generalized finite polynomial approximation (WINIMAX) to the reduced partition function of isotopic molecules

Abstract

The MINIMAX finite polynomial approximation to an arbitrary function has been generalized to include a weighting function (WINIMAX). It is suggested that an exponential is a reasonable weighting function for the logarithm of the reduced partition function of a harmonic oscillator. Comparison of the error function for finite orthogonal polynomial (FOP), MINIMAX, and WINIMAX expansions of the logarithm of the reduced vibrational partition function show WINIMAX to be the best of the three approximations. A condensed table of WINIMAX coefficients is presented. The FOP, MINIMAX, and WINIMAX approximations are compared with exact calculations of the logarithm of the reduced partition function ratios for isotopic substitution in H2O, CH4, CH2O, C2H4, and C2H6 at 300 °K. Both deuterium and heavy atom isotope substitution are studied. Except for a third order expansion involving deuterium substitution, the WINIMAX method is superior to FOP and MINIMAX. At the level of a second order expansion WINIMAX approximations to ln(s/s′) f are good to 2.5% and 6.5% for deuterium and heavy atom substitution, respectively.