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Title: Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes

In earlier work [A. Y. Sokolov and G. K.-L. Chan, J. Chem. Phys. 144, 064102 (2016)], we introduced a time-dependent formulation of the second-order N-electron valence perturbation theory (t-NEVPT2) which (i) had a lower computational scaling than the usual internally contracted perturbation formulation and (ii) yielded the fully uncontracted NEVPT2 energy. We present a combination of t-NEVPT2 with a matrix product state (MPS) reference wavefunction (t-MPS-NEVPT2) that allows us to compute uncontracted dynamic correlation energies for large active spaces and basis sets, using the time-dependent density matrix renormalization group algorithm. In addition, we report a low-scaling MPS-based implementation of strongly contracted NEVPT2 (sc-MPS-NEVPT2) that avoids computation of the four-particle reduced density matrix. We use these new methods to compute the dissociation energy of the chromium dimer and to study the low-lying excited states in all-trans polyenes (C 4H 6 to C 24H 26), incorporating dynamic correlation for reference wavefunctions with up to 24 active electrons and orbitals
Authors:
 [1] ;  [1] ; ORCiD logo [1] ;  [1]
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
Publication Date:
Grant/Contract Number:
SC0008624; SC0010530; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 24; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Princeton Univ., NJ (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Contributing Orgs:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; polymers; correlation energy; transition metals; chemical elements; excitation energies; matrix product state; time dependent formulation; dissociation energy; perturbation theory; density matrix renormalization group
OSTI Identifier:
1474039
Alternate Identifier(s):
OSTI ID: 1365432

Sokolov, Alexander Yu., Guo, Sheng, Ronca, Enrico, and Chan, Garnet Kin-Lic. Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes. United States: N. p., Web. doi:10.1063/1.4986975.
Sokolov, Alexander Yu., Guo, Sheng, Ronca, Enrico, & Chan, Garnet Kin-Lic. Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes. United States. doi:10.1063/1.4986975.
Sokolov, Alexander Yu., Guo, Sheng, Ronca, Enrico, and Chan, Garnet Kin-Lic. 2017. "Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes". United States. doi:10.1063/1.4986975. https://www.osti.gov/servlets/purl/1474039.
@article{osti_1474039,
title = {Time-dependent N-electron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and all-trans polyenes},
author = {Sokolov, Alexander Yu. and Guo, Sheng and Ronca, Enrico and Chan, Garnet Kin-Lic},
abstractNote = {In earlier work [A. Y. Sokolov and G. K.-L. Chan, J. Chem. Phys. 144, 064102 (2016)], we introduced a time-dependent formulation of the second-order N-electron valence perturbation theory (t-NEVPT2) which (i) had a lower computational scaling than the usual internally contracted perturbation formulation and (ii) yielded the fully uncontracted NEVPT2 energy. We present a combination of t-NEVPT2 with a matrix product state (MPS) reference wavefunction (t-MPS-NEVPT2) that allows us to compute uncontracted dynamic correlation energies for large active spaces and basis sets, using the time-dependent density matrix renormalization group algorithm. In addition, we report a low-scaling MPS-based implementation of strongly contracted NEVPT2 (sc-MPS-NEVPT2) that avoids computation of the four-particle reduced density matrix. We use these new methods to compute the dissociation energy of the chromium dimer and to study the low-lying excited states in all-trans polyenes (C4H6 to C24H26), incorporating dynamic correlation for reference wavefunctions with up to 24 active electrons and orbitals},
doi = {10.1063/1.4986975},
journal = {Journal of Chemical Physics},
number = 24,
volume = 146,
place = {United States},
year = {2017},
month = {6}
}

Works referenced in this record:

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993
  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913