Timedependent Nelectron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and alltrans polyenes
In earlier work [A. Y. Sokolov and G. K.L. Chan, J. Chem. Phys. 144, 064102 (2016)], we introduced a timedependent formulation of the secondorder Nelectron valence perturbation theory (tNEVPT2) 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 tNEVPT2 with a matrix product state (MPS) reference wavefunction (tMPSNEVPT2) that allows us to compute uncontracted dynamic correlation energies for large active spaces and basis sets, using the timedependent density matrix renormalization group algorithm. In addition, we report a lowscaling MPSbased implementation of strongly contracted NEVPT2 (scMPSNEVPT2) that avoids computation of the fourparticle reduced density matrix. We use these new methods to compute the dissociation energy of the chromium dimer and to study the lowlying excited states in alltrans polyenes (C _{4}H _{6} to C _{24}H _{26}), incorporating dynamic correlation for reference wavefunctions with up to 24 active electrons and orbitals
 Authors:

^{[1]};
^{[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; AC0205CH11231
 Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 146; Journal Issue: 24; Journal ID: ISSN 00219606
 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) (SC22). 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 KinLic. Timedependent Nelectron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and alltrans polyenes. United States: N. p.,
Web. doi:10.1063/1.4986975.
Sokolov, Alexander Yu., Guo, Sheng, Ronca, Enrico, & Chan, Garnet KinLic. Timedependent Nelectron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and alltrans polyenes. United States. doi:10.1063/1.4986975.
Sokolov, Alexander Yu., Guo, Sheng, Ronca, Enrico, and Chan, Garnet KinLic. 2017.
"Timedependent Nelectron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and alltrans polyenes". United States.
doi:10.1063/1.4986975. https://www.osti.gov/servlets/purl/1474039.
@article{osti_1474039,
title = {Timedependent Nelectron valence perturbation theory with matrix product state reference wavefunctions for large active spaces and basis sets: Applications to the chromium dimer and alltrans polyenes},
author = {Sokolov, Alexander Yu. and Guo, Sheng and Ronca, Enrico and Chan, Garnet KinLic},
abstractNote = {In earlier work [A. Y. Sokolov and G. K.L. Chan, J. Chem. Phys. 144, 064102 (2016)], we introduced a timedependent formulation of the secondorder Nelectron valence perturbation theory (tNEVPT2) 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 tNEVPT2 with a matrix product state (MPS) reference wavefunction (tMPSNEVPT2) that allows us to compute uncontracted dynamic correlation energies for large active spaces and basis sets, using the timedependent density matrix renormalization group algorithm. In addition, we report a lowscaling MPSbased implementation of strongly contracted NEVPT2 (scMPSNEVPT2) that avoids computation of the fourparticle reduced density matrix. We use these new methods to compute the dissociation energy of the chromium dimer and to study the lowlying excited states in alltrans 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
journal, April 1993
 Becke, Axel D.
 The Journal of Chemical Physics, Vol. 98, Issue 7, p. 56485652