Fast evaluation of scaled opposite spin second-order Møller-Plesset correlation energies using auxiliary basis expansions and exploiting sparsity.
The scaled opposite spin Møller-Plesset method (SOS-MP2) is an economical way of obtaining correlation energies that are computationally cheaper, and yet, in a statistical sense, of higher quality than standard MP2 theory, by introducing one empirical parameter. But SOS-MP2 still has a fourth-order scaling step that makes the method inapplicable to very large molecular systems. We reduce the scaling of SOS-MP2 by exploiting the sparsity of expansion coefficients and local integral matrices, by performing local auxiliary basis expansions for the occupied-virtual product distributions. To exploit sparsity of 3-index local quantities, we use a blocking scheme in which entire zero-rows and columns, for a given third global index, are deleted by comparison against a numerical threshold. This approach minimizes sparse matrix book-keeping overhead, and also provides sufficiently large submatrices after blocking, to allow efficient matrix-matrix multiplies. The resulting algorithm is formally cubic scaling, and requires only moderate computational resources (quadratic memory and disk space) and, in favorable cases, is shown to yield effective quadratic scaling behavior in the size regime we can apply it to. Errors associated with local fitting using the attenuated Coulomb metric and numerical thresholds in the blocking procedure are found to be insignificant in terms of the predicted relative energies. A diverse set of test calculations shows that the size of system where significant computational savings can be achieved depends strongly on the dimensionality of the system, and the extent of localizability of the molecular orbitals.
Jung
Yousung
Y
Department of Chemistry, University of California, Berkeley, California 94720, USA.
Shao
Yihan
Y
Head-Gordon
Martin
M