Correlation of zero-point energy with molecular structure and molecular forces. 1. Development of the approximation

An approximation formula for the zero-point energy (ZPE) has been developed on the basis of Lanczos' tau method in which the ZPE has been expressed in terms of the traces of positive integral powers of the FG matrix. It requires two approximation parameters, i.e., a normalization reference point in a domain of vibration eigenvalues and a range for the purpose of expansion. These parameters have been determined for two special cases as well as for general situation at various values of a weighting function parameter. The approximation method has been tested on water, carbon dioxide, formaldehyde, and methane. The relative errors are 3% or less for the molecules examined, and the best choice of the parameters moderately depends on the frequency distribution. 25 references, 2 figures, 9 tables