Accurate and Efficient Parallel Implementation of an Effective Linear-Scaling Direct Random Phase Approximation Method

Graf, Daniel; Beuerle, Matthias; Schurkus, Henry F.; Luenser, Arne; Savasci, Goekcen und Ochsenfeld, Christian (2018): Accurate and Efficient Parallel Implementation of an Effective Linear-Scaling Direct Random Phase Approximation Method. In: Journal of Chemical Theory and Computation, Bd. 14, Nr. 5: S. 2505-2515

Abstract

An efficient algorithm for calculating the random phase approximation (RPA) correlation energy is presented that is as accurate as the canonical molecular orbital resolution-of-the identity RPA (RI-RPA) with the important advantage of an effective linear-scaling behavior (instead of quartic) for large systems due to a formulation in the local atomic orbital space. The high accuracy is achieved by utilizing optimized minimax integration schemes and the local Coulomb metric attenuated by the complementary error function for the RI approximation. The memory bottleneck of former atomic orbital (AO)-RI-RPA implementations (Schurkus, H. F.;Ochsenfeld, C. J. Chem. Phys. 2016, 144, 031101 and Luenser, A.;Schurkus, H. F.;Ochsenfeld, C. J. Chem. Theory Comput. 2017, 13, 1647-1655) is addressed by precontraction of the large 3-center integral matrix with the Cholesky factors of the ground state density reducing the memory requirements of that matrix by a factor of N-basis/N-occ Furthermore, we present a parallel implementation of our method, which not only leads to faster RPA correlation energy calculations but also to a scalable decrease in memory requirements, opening the door for investigations of large molecules even on small- to medium-sized computing clusters. Although it is known that AO methods are highly efficient for extended systems, where sparsity allows for reaching the linear-scaling regime, we show that our work also extends the applicability when considering highly delocalized systems for which no linear scaling can be achieved. As an example, the interlayer distance of two covalent organic framework pore fragments (comprising 384 atoms in total) is analyzed.

• Dokumententyp: Zeitschriftenartikel
• Fakultätsübergreifende Einrichtungen: Center for Integrated Protein Science Munich (CIPSM)
• Themengebiete: 500 Naturwissenschaften und Mathematik > 540 Chemie
• ISSN: 1549-9618
• Sprache: Englisch