REMOVAL OF DEPENDENCIES FROM NEARLY COMPLETE BASIS SETS - CALCULATIONS ON THE HELIUM DIMER

摘要

A method is devised for dealing with almost linearly dependent basis sets that contain large sets of bond functions. Using the largest of such basis sets, LARSAT, the second-order Moller-Plesset polarization dispersion energy of the helium dimer is calculated to be -17.08 K at R = 5.6 bohrs. MR-SDCI calculations, employing a set of 37 reference configurations, were performed for the helium dimer with several basis sets at 4.0 and 5.6 bohrs. Size-extensivity corrections were included to take into account the R dependency of the size-extensivity error in MR-SDCI calculations. The He-2 interaction energies computed with basis LARSAT are -10.92 K at 5.6 bohrs and 295.1 K at 4.0 bohrs. The 37-MR-SDCI calculations with basis LARSAT almost reproduce the He-2 full configuration interaction (CI) interaction energies computed with the same basis, at notably smaller cost. (C) 1997 John Wiley & Sons, Inc. [References: 39]