General orbital invariant MP2-F12 theory.

A general form of orbital invariant explicitly correlated second-order closed-shell Moller-Plesset perturbation theory (MP2-F12) is derived, and compact working equations are presented. Many-electron integrals are avoided by resolution of the identity (RI) approximations using the complementary auxiliary basis set approach. A hierarchy of well defined levels of approximation is introduced, differing from the exact theory by the neglect of terms involving matrix elements over the Fock operator. The most accurate method is denoted as MP2-F12/3B. This assumes only that Fock matrix elements between occupied orbitals and orbitals outside the auxiliary basis set are negligible. For the chosen ansatz for the first-order wave function this is exact if the auxiliary basis is complete. In the next lower approximation it is assumed that the occupied orbital space is closed under action of the Fock operator [generalized Brillouin condition (GBC)]; this is equivalent to approximation 2B of Klopper and Samson [J. Chem. Phys. 116, 6397 (2002)]. Further approximations can be introduced by assuming the extended Brillouin condition (EBC) or by neglecting certain terms involving the exchange operator. A new approximation MP2-F12/3C, which is closely related to the MP2-R12/C method recently proposed by Kedzuch et al. [Int. J. Quantum Chem. 105, 929 (2005)] is described. In the limit of a complete RI basis this method is equivalent to MP2-F12/3B. The effect of the various approximations (GBC, EBC, and exchange) is tested by studying the convergence of the correlation energies with respect to the atomic orbital and auxiliary basis sets for 21 molecules. The accuracy of relative energies is demonstrated for 16 chemical reactions. Approximation 3C is found to perform equally well as the computationally more demanding approximation 3B. The reaction energies obtained with smaller basis sets are found to be most accurate if the orbital-variant diagonal Ansatz combined with localized orbitals is used for the first-order wave function. This unexpected result is attributed to geminal basis set superposition errors present in the formally more rigorous orbital invariant methods.