An integral-factorized implementation of the driven similarity renormalization group second-order multireference perturbation theory

Abstract

We report an efficient implementation of a second-order multireference perturbation theory based on the driven similarity renormalization group (DSRG-MRPT2) [C. Li and F. A. Evangelista, J. Chem. Theory Comput. 11, 2097 (2015)]. Our implementation employs factorized two-electron integrals to avoid storage of large four-index intermediates. It also exploits the block structure of the reference density matrices to reduce the computational cost to that of second-order Møller$-$Plesset perturbation theory. Our new DSRG-MRPT2 implementation is benchmarked on ten naphthyne isomers using basis sets up to quintuple-$\zeta$ quality. We find that the singlet-triplet splittings (${\Delta }_{\text{ST}}$) of the naphthyne isomers strongly depend on the equilibrium structures. For a consistent set of geometries, the ${\Delta }_{\text{ST}}$ values predicted by the DSRG-MRPT2 are in good agreements with those computed by the reduced multireference coupled cluster theory with singles, doubles, and perturbative triples.

References in corpus (10)

• The In-Medium Similarity Renormalization Group: A Novel Ab Initio Method for Nuclei
• Similarity Renormalization Group for Nucleon-Nucleon Interactions
• The density matrix renormalization group for ab initio quantum chemistry
• In-Medium Similarity Renormalization Group for Nuclei
• Evolution of Nuclear Many-Body Forces with the Similarity Renormalization Group
• In-Medium Similarity Renormalization Group for Open-Shell Nuclei
• A canonical transformation theory from extended normal ordering
• Ab Initio Multi-Reference In-Medium Similarity Renormalization Group Calculations of Even Calcium and Nickel Isotopes
• A numerical canonical transformation approach to quantum many body problems
• A driven similarity renormalization group approach to quantum many-body problems

Cited by in corpus (8)

• The Density Matrix Renormalization Group in Chemistry and Molecular Physics: Recent Developments and New Challenges
• Multi-reference perturbation theory with Cholesky decomposition for the density matrix renormalization group
• In-Medium Similarity Renormalization Group for Closed and Open-Shell Nuclei
• Driven similarity renormalization group: Third-order multireference perturbation theory
• Spin-free formulation of the multireference driven similarity renormalization group: A benchmark study of first-row diatomic molecules and spin-crossover energetics
• Simulating X-ray Photoelectron Spectra With Strong Electron Correlation Using Multireference Algebraic Diagrammatic Construction Theory
• A Combined Selected Configuration Interaction and Many-Body Treatment of Static and Dynamical Correlation in Oligoacenes
• Improving the efficiency of the multireference driven similarity renormalization group via sequential transformation, density fitting, and the non-interacting virtual orbital approximation