PNO-CI and PNO-CEPA studies of electron correlation effects

Abstract

Abstract Dipole moments and static dipole polarizabilities are calculated for neon and the molecules HF, H2O, NH3, CH4 and CO from SCF and correlated wavefunctions. The construction of appropriate gaussian-type basis sets is discussed and the convergence of the correlation contributions to the polarizability is analysed. The effect of vibrational averaging is also investigated. The polarizabilities as obtained from the coupled electron pair approximation (CEPA) with the most extended basis sets differ from experimental values by less than 1·5 per cent in all cases. The calculated polarizability anisotropies appear to be correct to about 5–15 per cent. The correlation contributions to the polarizabilities are found to vary from 3 to 12 per cent.