Correlation energy extrapolation by intrinsic scaling. II. The water and the nitrogen molecule.
The extrapolation method for determining benchmark quality full configuration-interaction energies described in preceding paper [L. Bytautas and K. Ruedenberg, J. Chem. Phys. 121, 10905 (2004)] is applied to the molecules H(2)O and N(2). As in the neon atom case, discussed in preceding paper [L. Bytautas and K. Ruedenberg, J. Chem. Phys. 121, 10905 (2004)] remarkably accurate scaling relations are found to exist between the correlation energy contributions from various excitation levels of the configuration-interaction approach, considered as functions of the size of the correlating orbital space. The method for extrapolating a sequence of smaller configuration-interaction calculations to the full configuration-interaction energy and for constructing compact accurate configuration-interaction wave functions is also found to be effective for these molecules. The results are compared with accurate ab initio methods, such as many-body perturbation theory, coupled-cluster theory, as well as with variational calculations wherever possible.
Bytautas
Laimutis
L
Department of Chemistry and Ames Laboratory/USDOE, Iowa State University, Ames, IA 50011, USA.
Ruedenberg
Klaus
K