Efficient Reduced-Scaling Second-Order Møller–Plesset Perturbation Theory with Cholesky-Decomposed Densities and an Attenuated Coulomb Metric
| Autor: | Christian Ochsenfeld, Daniel Graf, Michael Glasbrenner |
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| Rok vydání: | 2020 |
| Předmět: |
Physics
010304 chemical physics Electric potential energy Møller–Plesset perturbation theory Basis function 01 natural sciences Computer Science Applications 0103 physical sciences Metric (mathematics) Physics::Atomic and Molecular Clusters Coulomb Statistical physics Physical and Theoretical Chemistry Perturbation theory Scaling Cholesky decomposition |
| Zdroj: | Journal of Chemical Theory and Computation. 16:6856-6868 |
| ISSN: | 1549-9626 1549-9618 |
| DOI: | 10.1021/acs.jctc.0c00600 |
| Popis: | We present a novel, highly efficient method for the computation of second-order Moller-Plesset perturbation theory (MP2) correlation energies, which uses the resolution of the identity (RI) approximation and local molecular orbitals obtained from a Cholesky decomposition of pseudodensity matrices (CDD), as in the RI-CDD-MP2 method developed previously in our group [Maurer, S. A.; Clin, L.; Ochsenfeld, C. J. Chem. Phys. 2014, 140, 224112]. In addition, we introduce an attenuated Coulomb metric and subsequently redesign the RI-CDD-MP2 method in order to exploit the resulting sparsity in the three-center integrals. Coulomb and exchange energy contributions are computed separately using specialized algorithms. A simple, yet effective integral screening protocol based on Schwarz estimates is used for the MP2 exchange energy. The Coulomb energy computation and the preceding transformations of the three-center integrals are accelerated using a modified version of the natural blocking approach [Jung, Y.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2006, 8, 2831-2840]. Effective subquadratic scaling for a wide range of molecule sizes is demonstrated in test calculations in conjunction with a low prefactor. The method is shown to enable cost-efficient MP2 calculations on large molecular systems with several thousand basis functions. |
| Databáze: | OpenAIRE |
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