Extrapolation of electron correlation energies to finite and complete basis set targets

Abstract

The electron correlation energy of two-electron atoms is known to converge asymptotically as approximately (L+1)(-3) to the complete basis set limit, where L is the maximum angular momentum quantum number included in the basis set. Numerical evidence has established a similar asymptotic convergence approximately X(-3) with the cardinal number X of correlation-consistent basis sets cc-pVXZ for coupled cluster singles and doubles (CCSD) and second order perturbation theory (MP2) calculations of molecules. The main focus of this article is to probe for deviations from asymptotic convergence behavior for practical values of X by defining a trial function X(-beta) that for an effective exponent beta=beta(eff)(X,X+1,X+N) provides the correct energy E(X+N), when extrapolating from results for two smaller basis sets, E(X) and E(X+1). This analysis is first applied to "model" expansions available from analytical theory, and then to a large body of finite basis set results (X=D,T,Q,5,6) for 105 molecules containing H, C, N, O, and F, complemented by a smaller set of 14 molecules for which accurate complete basis set limits are available from MP2-R12 and CCSD-R12 calculations. beta(eff) is generally found to vary monotonically with the target of extrapolation, X+N, making results for large but finite basis sets a useful addition to the limited number of cases where complete basis set limits are available. Significant differences in effective convergence behavior are observed between MP2 and CCSD (valence) correlation energies, between hydrogen-rich and hydrogen-free molecules, and, for He, between partial-wave expansions and correlation-consistent basis sets. Deviations from asymptotic convergence behavior tend to get smaller as X increases, but not always monotonically, and are still quite noticeable even for X=5. Finally, correlation contributions to atomization energies (rather than total energies) exhibit a much larger variation of effective convergence behavior, and extrapolations from small basis sets are found to be particularly erratic for molecules containing several electronegative atoms. Observed effects are discussed in the light of results known from analytical theory. A carefully calibrated protocol for extrapolations to the complete basis set limit is presented, based on a single "optimal" exponent beta(opt)(X,X+1,infinity) for the entire set of molecules, and compared to similar approaches reported in the literature.