Explicitly correlated local second-order perturbation theory with a frozen geminal correlation factor

The recently introduced MP2-R12/2(*)A(loc) and LMP2-R12/2(*)A(loc) methods are modified to use a short-range correlation factor expanded as a fixed linear combination of Gaussian geminals. Density fitting is used to reduce the effort for integral evaluation, and local approximations are introduced to improve the scaling of the computational resources with molecular size. The MP2-F12/2(*)A(loc) correlation energies converge very rapidly with respect to the atomic orbital basis set size. Already with the aug-cc-pVTZ basis the correlation energies computed for a set of 21 small molecules are found to be within 0.5% of the MP2 basis set limit. Furthermore the short-range correlation factor leads to an improved convergence of the resolution of the identity, and eliminates problems with long-range errors in density fitting caused by the linear r(12) factor. The DF-LMP2-F12/2(*)A(loc) method is applied to compute second-order correlation energies for molecules with up to 49 atoms and more than 1600 basis functions. (c) 2006 American Institute of Physics.