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Title: Complex absorbing potentials within EOM-CC family of methods: Theory, implementation, and benchmarks

Abstract

A production-level implementation of equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) for electron attachment and excitation energies augmented by a complex absorbing potential (CAP) is presented. The new method enables the treatment of metastable states within the EOM-CC formalism in a similar manner as bound states. The numeric performance of the method and the sensitivity of resonance positions and lifetimes to the CAP parameters and the choice of one-electron basis set are investigated. A protocol for studying molecular shape resonances based on the use of standard basis sets and a universal criterion for choosing the CAP parameters are presented. Our results for a variety of π{sup *} shape resonances of small to medium-size molecules demonstrate that CAP-augmented EOM-CCSD is competitive relative to other theoretical approaches for the treatment of resonances and is often able to reproduce experimental results.

Authors:
; ;  [1];  [2];  [1];  [3];  [3];  [4]; ;  [5]
  1. Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482 (United States)
  2. Department of Chemistry, Boston University, Boston, Massachusetts 02215-2521 (United States)
  3. (United States)
  4. Q-Chem, Inc., 6601 Owens Drive, Suite 105 Pleasanton, California 94588 (United States)
  5. Department of Chemistry, University of California, Berkeley, California 94720 (United States)
Publication Date:
OSTI Identifier:
22308766
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 2; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BOUND STATE; ELECTRON ATTACHMENT; ELECTRONS; EQUATIONS OF MOTION; EXCITATION; METASTABLE STATES; MOLECULES; RESONANCE; SENSITIVITY

Citation Formats

Zuev, Dmitry, Jagau, Thomas-C., Krylov, Anna I., Bravaya, Ksenia B., Epifanovsky, Evgeny, Department of Chemistry, University of California, Berkeley, California 94720, Q-Chem, Inc., 6601 Owens Drive, Suite 105 Pleasanton, California 94588, Shao, Yihan, Sundstrom, Eric, and Head-Gordon, Martin. Complex absorbing potentials within EOM-CC family of methods: Theory, implementation, and benchmarks. United States: N. p., 2014. Web. doi:10.1063/1.4885056.
Zuev, Dmitry, Jagau, Thomas-C., Krylov, Anna I., Bravaya, Ksenia B., Epifanovsky, Evgeny, Department of Chemistry, University of California, Berkeley, California 94720, Q-Chem, Inc., 6601 Owens Drive, Suite 105 Pleasanton, California 94588, Shao, Yihan, Sundstrom, Eric, & Head-Gordon, Martin. Complex absorbing potentials within EOM-CC family of methods: Theory, implementation, and benchmarks. United States. doi:10.1063/1.4885056.
Zuev, Dmitry, Jagau, Thomas-C., Krylov, Anna I., Bravaya, Ksenia B., Epifanovsky, Evgeny, Department of Chemistry, University of California, Berkeley, California 94720, Q-Chem, Inc., 6601 Owens Drive, Suite 105 Pleasanton, California 94588, Shao, Yihan, Sundstrom, Eric, and Head-Gordon, Martin. Mon . "Complex absorbing potentials within EOM-CC family of methods: Theory, implementation, and benchmarks". United States. doi:10.1063/1.4885056.
@article{osti_22308766,
title = {Complex absorbing potentials within EOM-CC family of methods: Theory, implementation, and benchmarks},
author = {Zuev, Dmitry and Jagau, Thomas-C. and Krylov, Anna I. and Bravaya, Ksenia B. and Epifanovsky, Evgeny and Department of Chemistry, University of California, Berkeley, California 94720 and Q-Chem, Inc., 6601 Owens Drive, Suite 105 Pleasanton, California 94588 and Shao, Yihan and Sundstrom, Eric and Head-Gordon, Martin},
abstractNote = {A production-level implementation of equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) for electron attachment and excitation energies augmented by a complex absorbing potential (CAP) is presented. The new method enables the treatment of metastable states within the EOM-CC formalism in a similar manner as bound states. The numeric performance of the method and the sensitivity of resonance positions and lifetimes to the CAP parameters and the choice of one-electron basis set are investigated. A protocol for studying molecular shape resonances based on the use of standard basis sets and a universal criterion for choosing the CAP parameters are presented. Our results for a variety of π{sup *} shape resonances of small to medium-size molecules demonstrate that CAP-augmented EOM-CCSD is competitive relative to other theoretical approaches for the treatment of resonances and is often able to reproduce experimental results.},
doi = {10.1063/1.4885056},
journal = {Journal of Chemical Physics},
number = 2,
volume = 141,
place = {United States},
year = {Mon Jul 14 00:00:00 EDT 2014},
month = {Mon Jul 14 00:00:00 EDT 2014}
}