Accurate Pair Interaction Energies for Helium from Supermolecular Gaussian Geminal Calculations

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 111; no. 31; pp. 7611 - 7623
• Main Authors: Patkowski, Konrad, Cencek, Wojciech, Jeziorska, Małgorzata, Jeziorski, Bogumił, Szalewicz, Krzysztof
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 09.08.2007
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp071437x

Nonrelativistic clamped-nuclei pair interaction energy for ground-state helium atoms has been computed for 12 interatomic separations ranging from 3.0 to 9.0 bohr. The calculations applied the supermolecular approach. The major part of the interaction energy was obtained using the Gaussian geminal implementation of the coupled-cluster theory with double excitations (CCD). Relatively small contributions from single, triple, and quadruple excitations were subsequently included employing the conventional orbital coupled-cluster method with single, double, and noniterative triple excitations [CCSD(T)] and the full configuration interaction (FCI) method. For three distances, the single-excitation contribution was taken from literature Gaussian-geminal calculations at the CCSD level. The orbital CCSD(T) and FCI calculations used very large basis sets, up to doubly augmented septuple- and sextuple-zeta size, respectively, and were followed by extrapolations to the complete basis set limits. The accuracy of the total interaction energies has been estimated to be about 3 mK or 0.03% at the minimum of the potential well. For the attractive part of the well, the relative errors remain consistently smaller than 0.03%. In the repulsive part, the accuracy is even better, except, of course, for the region where the potential goes through zero. For interatomic separations smaller than 4.0 bohr, the relative errors do not exceed 0.01%. Such uncertainties are significantly smaller than the expected values of the relativistic and diagonal Born−Oppenheimer contributions to the potential.