Extrapolating to the one-electron basis-set limit in electronic structure calculations

A simple, yet reliable, scheme based on treating uniformly singlet-pair and triplet-pair interactions is suggested to extrapolate atomic and molecular electron correlation energies calculated at two basis-set levels of ab initio theory to the infinite one-electron basis-set limit. The novel dual-level method is first tested on extrapolating the full correlation in single-reference coupled-cluster singles and doubles energies for the closed-shell systems CH2((1)A(1)), H2O, HF, N-2, CO, Ne, and F-2 with correlation-consistent basis sets of the type cc-pVXZ (X=D,T,Q,5,6) reported by Klopper [Mol. Phys. 6, 481 (2001)] against his own benchmark calculations with large uncontracted basis sets obtained from explicit correlated singles and doubles coupled-cluster theory. Comparisons are also reported for the same data set but using both single-reference Moller-Plesset and coupled-cluster doubles methods. The results show a similar, often better, accordance with the target results than Klopper's extrapolations where singlet-pair and triplet-pair energies are extrapolated separately using the popular X-3 and X-5 dual-level laws, respectively. Applications to the extrapolation of the dynamical correlation in multireference configuration interaction calculations carried out anew for He, H-2, HeH+, He-2(++), H-3(+)(1 (1)A(')), H-3(+)(1 (3)A(')), BH, CH, NH, OH, FH, B-2, C-2, N-2, O-2, F-2, BO, CO, NO, BN, CN, SH, H2O, and NH3 with standard augmented correlation-consistent basis sets of the type aug-cc-pVXZ (X=D,T,Q,5,6) are also reported. Despite lacking accurate theoretical or experimental data for comparison in the case of most diatomic systems, the new method also shows in this case a good performance when judged from the results obtained with the traditional schemes which extrapolate using the two largest affordable basis sets. For the Hartree-Fock and complete-active space self-consistent field energies, a simple pragmatic extrapolation rule is examined whose results are shown to compare well with the ones obtained from the best reported schemes. (c) 2007 American Institute of Physics.