Quasi-degenerate perturbation theory using matrix product states

The Journal of Chemical Physics
Sandeep SharmaAli Alavi

Abstract

In this work, we generalize the recently proposed matrix product state perturbation theory (MPSPT) for calculating energies of excited states using quasi-degenerate (QD) perturbation theory. Our formulation uses the Kirtman-Certain-Hirschfelder canonical Van Vleck perturbation theory, which gives Hermitian effective Hamiltonians at each order, and also allows one to make use of Wigner's 2n + 1 rule. Further, our formulation satisfies Granovsky's requirement of model space invariance which is important for obtaining smooth potential energy curves. Thus, when we use MPSPT with the Dyall Hamiltonian, we obtain a model space invariant version of quasi-degenerate n-electron valence state perturbation theory (NEVPT), a property that the usual formulation of QD-NEVPT2 based on a multipartitioning technique lacked. We use our method on the benchmark problems of bond breaking of LiF which shows ionic to covalent curve crossing and the twist around the double bond of ethylene where significant valence-Rydberg mixing occurs in the excited states. In accordance with our previous work, we find that multi-reference linearized coupled cluster theory is more accurate than other multi-reference theories of similar cost.

References

Nov 9, 1992·Physical Review Letters·S R White
Jul 13, 2002·Journal of Computational Chemistry·Haruyuki NakanoKimihiko Hirao
Aug 31, 2004·The Journal of Chemical Physics·Celestino AngeliRenzo Cimiraglia
Jan 11, 2005·The Journal of Chemical Physics·Gerrit MoritzMarkus Reiher
Jan 15, 2008·The Journal of Chemical Physics·Dominika Zgid, Marcel Nooijen
May 27, 2009·The Journal of Chemical Physics·Dominika ZgidGarnet Kin-Lic Chan
Jan 12, 2011·Annual Review of Physical Chemistry·Garnet Kin-Lic Chan, Sandeep Sharma
Apr 3, 2012·The Journal of Chemical Physics·Sandeep Sharma, Garnet Kin-Lic Chan
Feb 2, 2013·Physical Review Letters·F R PetruzieloC J Umrigar
Sep 17, 2015·The Journal of Chemical Physics·Sandeep Sharma, Ali Alavi

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Citations

Aug 9, 2016·The Journal of Chemical Physics·Sebastian WoutersDimitri Van Neck
Jul 11, 2016·The Journal of Chemical Physics·Garnet Kin-Lic ChanSteven R White
Jan 18, 2017·Journal of Chemical Theory and Computation·Leon FreitagMarkus Reiher
Jan 7, 2017·Journal of Chemical Theory and Computation·Sandeep SharmaAli Alavi
Feb 6, 2017·The Journal of Chemical Physics·Guillaume JeanmairetAli Alavi
Dec 24, 2017·The Journal of Chemical Physics·Shubhrodeep PathakFrank Neese
Apr 1, 2019·The Journal of Chemical Physics·Stefan Behnle, Reinhold F Fink
Dec 12, 2019·The Journal of Chemical Physics·Ankit MahajanSandeep Sharma
Apr 2, 2018·The Journal of Chemical Physics·Chenyang Li, Francesco A Evangelista
Nov 4, 2020·The Journal of Chemical Physics·Alberto Baiardi, Markus Reiher
Jul 13, 2021·The Journal of Physical Chemistry Letters·Mattia BondanzaBenedetta Mennucci
Aug 7, 2021·Physical Chemistry Chemical Physics : PCCP·Abhishek Khedkar, Michael Roemelt
Oct 3, 2017·Journal of Chemical Theory and Computation·James E T SmithSandeep Sharma
Dec 5, 2017·Journal of Chemical Theory and Computation·Bastien Mussard, Sandeep Sharma
Jul 25, 2018·Chemical Reviews·Hans LischkaMario Barbatti
Mar 30, 2018·Journal of Chemical Theory and Computation·Tamara HuschMarkus Reiher
Feb 7, 2020·Journal of Chemical Theory and Computation·Stefano Battaglia, Roland Lindh

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