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Title: Driven similarity renormalization group: Third-order multireference perturbation theory

Here, a third-order multireference perturbation theory based on the driven similarity renormalization group (DSRG-MRPT3) approach is presented. The DSRG-MRPT3 method has several appealing features: (a) it is intruder free, (b) it is size consistent, (c) it leads to a non-iterative algorithm with O(N 6) scaling, and (d) it includes reference relaxation effects. The DSRG-MRPT3 scheme is benchmarked on the potential energy curves of F 2, H 2O 2, C 2H 6, and N 2 along the F–F, O–O, C–C, and N–N bond dissociation coordinates, respectively. The nonparallelism errors of DSRG-MRPT3 are consistent with those of complete active space third-order perturbation theory and multireference configuration interaction with singles and doubles and show significant improvements over those obtained from DSRG second-order multireference perturbation theory. Our efficient implementation of the DSRG-MRPT3 based on factorized electron repulsion integrals enables studies of medium-sized open-shell organic compounds. This point is demonstrated with computations of the singlet-triplet splitting (Δ ST = E T–E S) of 9,10-anthracyne. At the DSRG-MRPT3 level of theory, our best estimate of the adiabatic Δ ST is 3.9 kcal mol –1, a value that is within 0.1 kcal mol –1 from multireference coupled cluster results.
Authors:
ORCiD logo [1] ; ORCiD logo [1]
  1. Emory Univ., Atlanta, GA (United States)
Publication Date:
Grant/Contract Number:
SC0016004
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Emory Univ., Atlanta, GA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; driven similarity renormalization group; multireference theories; perturbation theory
OSTI Identifier:
1351290

Li, Chenyang, and Evangelista, Francesco A. Driven similarity renormalization group: Third-order multireference perturbation theory. United States: N. p., Web. doi:10.1063/1.4979016.
Li, Chenyang, & Evangelista, Francesco A. Driven similarity renormalization group: Third-order multireference perturbation theory. United States. doi:10.1063/1.4979016.
Li, Chenyang, and Evangelista, Francesco A. 2017. "Driven similarity renormalization group: Third-order multireference perturbation theory". United States. doi:10.1063/1.4979016. https://www.osti.gov/servlets/purl/1351290.
@article{osti_1351290,
title = {Driven similarity renormalization group: Third-order multireference perturbation theory},
author = {Li, Chenyang and Evangelista, Francesco A.},
abstractNote = {Here, a third-order multireference perturbation theory based on the driven similarity renormalization group (DSRG-MRPT3) approach is presented. The DSRG-MRPT3 method has several appealing features: (a) it is intruder free, (b) it is size consistent, (c) it leads to a non-iterative algorithm with O(N6) scaling, and (d) it includes reference relaxation effects. The DSRG-MRPT3 scheme is benchmarked on the potential energy curves of F2, H2O2, C2H6, and N2 along the F–F, O–O, C–C, and N–N bond dissociation coordinates, respectively. The nonparallelism errors of DSRG-MRPT3 are consistent with those of complete active space third-order perturbation theory and multireference configuration interaction with singles and doubles and show significant improvements over those obtained from DSRG second-order multireference perturbation theory. Our efficient implementation of the DSRG-MRPT3 based on factorized electron repulsion integrals enables studies of medium-sized open-shell organic compounds. This point is demonstrated with computations of the singlet-triplet splitting (ΔST = ET–ES) of 9,10-anthracyne. At the DSRG-MRPT3 level of theory, our best estimate of the adiabatic ΔST is 3.9 kcal mol–1, a value that is within 0.1 kcal mol–1 from multireference coupled cluster results.},
doi = {10.1063/1.4979016},
journal = {Journal of Chemical Physics},
number = 12,
volume = 146,
place = {United States},
year = {2017},
month = {3}
}