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Title: Excited states via coupled cluster theory without equation-of-motion methods: Seeking higher roots with application to doubly excited states and double core hole states

Abstract

In this work, we revisited the idea of using the coupled-cluster (CC) ground state formalism to target excited states. Our main focus was targeting doubly excited states and double core hole states. Typical equation-of-motion (EOM) approaches for obtaining these states struggle without higher-order excitations than doubles. We showed that by using a non-Aufbau determinant optimized via the maximum overlap method, the CC ground state solver can target higher energy states. Furthermore, just with singles and doubles (i.e., CCSD), we demonstrated that the accuracy of ΔCCSD and ΔCCSD(T) (triples) far surpasses that of EOM-CCSD for doubly excited states. The accuracy of ΔCCSD(T) is nearly exact for doubly excited states considered in this work. For double core hole states, we used an improved ansatz for greater numerical stability by freezing core hole orbitals. The improved methods, core valence separation (CVS)-ΔCCSD and CVS-ΔCCSD(T), were applied to the calculation of the double ionization potential of small molecules. Even without relativistic corrections, we observed qualitatively accurate results with CVS-ΔCCSD and CVS-ΔCCSD(T). Remaining challenges in ΔCC include the description of open-shell singlet excited states with the single-reference CC ground state formalism as well as excited states with genuine multireference character. The tools and intuition developed inmore » this work may serve as a stepping stone toward directly targeting arbitrary excited states using ground state CC methods.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1975812
Alternate Identifier(s):
OSTI ID: 1576805
Grant/Contract Number:  
AC02-05CH11231; ACO2-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 21; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; coupled-cluster methods; excitation energies; equations of motion

Citation Formats

Lee, Joonho, Small, David W., and Head-Gordon, Martin. Excited states via coupled cluster theory without equation-of-motion methods: Seeking higher roots with application to doubly excited states and double core hole states. United States: N. p., 2019. Web. doi:10.1063/1.5128795.
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Lee, Joonho, Small, David W., & Head-Gordon, Martin. Excited states via coupled cluster theory without equation-of-motion methods: Seeking higher roots with application to doubly excited states and double core hole states. United States. https://doi.org/10.1063/1.5128795
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Lee, Joonho, Small, David W., and Head-Gordon, Martin. Mon . "Excited states via coupled cluster theory without equation-of-motion methods: Seeking higher roots with application to doubly excited states and double core hole states". United States. https://doi.org/10.1063/1.5128795. https://www.osti.gov/servlets/purl/1975812.
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@article{osti_1975812,
title = {Excited states via coupled cluster theory without equation-of-motion methods: Seeking higher roots with application to doubly excited states and double core hole states},
author = {Lee, Joonho and Small, David W. and Head-Gordon, Martin},
abstractNote = {In this work, we revisited the idea of using the coupled-cluster (CC) ground state formalism to target excited states. Our main focus was targeting doubly excited states and double core hole states. Typical equation-of-motion (EOM) approaches for obtaining these states struggle without higher-order excitations than doubles. We showed that by using a non-Aufbau determinant optimized via the maximum overlap method, the CC ground state solver can target higher energy states. Furthermore, just with singles and doubles (i.e., CCSD), we demonstrated that the accuracy of ΔCCSD and ΔCCSD(T) (triples) far surpasses that of EOM-CCSD for doubly excited states. The accuracy of ΔCCSD(T) is nearly exact for doubly excited states considered in this work. For double core hole states, we used an improved ansatz for greater numerical stability by freezing core hole orbitals. The improved methods, core valence separation (CVS)-ΔCCSD and CVS-ΔCCSD(T), were applied to the calculation of the double ionization potential of small molecules. Even without relativistic corrections, we observed qualitatively accurate results with CVS-ΔCCSD and CVS-ΔCCSD(T). Remaining challenges in ΔCC include the description of open-shell singlet excited states with the single-reference CC ground state formalism as well as excited states with genuine multireference character. The tools and intuition developed in this work may serve as a stepping stone toward directly targeting arbitrary excited states using ground state CC methods.},
doi = {10.1063/1.5128795},
journal = {Journal of Chemical Physics},
number = 21,
volume = 151,
place = {United States},
year = {Mon Dec 02 00:00:00 EST 2019},
month = {Mon Dec 02 00:00:00 EST 2019}
}
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