TOPICAL REVIEW Highly accurate calculations of molecular electronic structure

Abstract. The highly accurate calculation of molecular electronic structure requires the expansion of the molecular electronic wavefunction to be as nearly complete as possible both in one- and n-electron space. In this review, we consider the convergence behaviour of computed electronic energies, in particular electronic enthalpies of reaction, as a function of the one-electron space. Based on the convergence behaviour, extrapolations to the limit of a complete one-electron basis are possible and such extrapolations are compared with the direct computation of electronic energies near the basis-set limit by means of explicitly correlated methods. The most elaborate and accurate computations are put into perspective with respect to standard and—from a computational point of view—inexpensive density functional, complete basis set (CBS) and Gaussian-2 calculations. Using the explicitly correlated coupled-cluster method including singles, doubles and non-iterative triples replacements, it is possible to compute (the electronic part of) enthalpies of reaction accurate to within 1 kJ mol−1. To achieve this level of accuracy with standard coupled-cluster methods, large basis sets or extrapolations to the basis-set limit are necessary to exploit fully the intrinsic accuracy of the coupled-cluster methods