Gaussian-1 theory: A general procedure for prediction of molecular energies

Abstract

A general procedure is developed for the computation of the total energies of molecules at their equilibrium geometries. Ab initio molecular orbital theory is used to calculate electronic energies by a composite method, utilizing large basis sets (including diffuse-sp, double-d and f-polarization functions) and treating electron correlation by Mo/ller–Plesset perturbation theory and by quadratic configuration interaction. The theory is also used to compute zero-point vibrational energy corrections. Total atomization energies for a set of 31 molecules are found to agree with experimental thermochemical data to an accuracy greater than 2 kcal mol−1 in most cases. Similar agreement is achieved for ionization energies, electron and proton affinities. Residual errors are assessed for the total energies of neutral atoms.