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

A method is devised for dealing with almost linearly dependent basis s ets that contain large sets of bond functions. Using the largest of su ch basis sets, LARSAT, the second-order Moller-Plesset polarization di spersion 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 con figurations, were performed for the helium dimer with several basis se ts 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 M R-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 con figuration interaction (CI) interaction energies computed with the sam e basis, at notably smaller cost. (C) 1997 John Wiley & Sons, Inc.