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Title: Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine

Abstract

A theoretical approach for calculating core-level states in condensed phase is presented. The approach is based on equation-of-motion coupled-cluster theory (EOMCC) and effective fragment potential (EFP) method. By introducing an approximate treatment of double excitations in the EOM-CCSD (EOM-CC with single and double substitutions) ansatz, we address poor convergence issues that are encountered for the core-level states and significantly reduce computational costs. While the approximations introduce relatively large errors in the absolute values of transition energies, the errors are systematic. Consequently, chemical shifts, changes in ionization energies relative to reference systems, are reproduced reasonably well. By using different protonation forms of solvated glycine as a benchmark system, we show that our protocol is capable of reproducing the experimental chemical shifts with a quantitative accuracy. The results demonstrate that chemical shifts are very sensitive to the solvent interactions and that explicit treatment of solvent, such as EFP, is essential for achieving quantitative accuracy.

Authors:
ORCiD logo [1];  [1]
  1. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1367515
Alternate Identifier(s):
OSTI ID: 1368601
Grant/Contract Number:  
FG02-05ER15685
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 1; 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; Biomolecules; Chemical reactions; Coupled cluster; Basis sets; Many body problems

Citation Formats

Sadybekov, Arman, and Krylov, Anna I. Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine. United States: N. p., 2017. Web. doi:10.1063/1.4990564.
Sadybekov, Arman, & Krylov, Anna I. Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine. United States. doi:10.1063/1.4990564.
Sadybekov, Arman, and Krylov, Anna I. Fri . "Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine". United States. doi:10.1063/1.4990564. https://www.osti.gov/servlets/purl/1367515.
@article{osti_1367515,
title = {Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine},
author = {Sadybekov, Arman and Krylov, Anna I.},
abstractNote = {A theoretical approach for calculating core-level states in condensed phase is presented. The approach is based on equation-of-motion coupled-cluster theory (EOMCC) and effective fragment potential (EFP) method. By introducing an approximate treatment of double excitations in the EOM-CCSD (EOM-CC with single and double substitutions) ansatz, we address poor convergence issues that are encountered for the core-level states and significantly reduce computational costs. While the approximations introduce relatively large errors in the absolute values of transition energies, the errors are systematic. Consequently, chemical shifts, changes in ionization energies relative to reference systems, are reproduced reasonably well. By using different protonation forms of solvated glycine as a benchmark system, we show that our protocol is capable of reproducing the experimental chemical shifts with a quantitative accuracy. The results demonstrate that chemical shifts are very sensitive to the solvent interactions and that explicit treatment of solvent, such as EFP, is essential for achieving quantitative accuracy.},
doi = {10.1063/1.4990564},
journal = {Journal of Chemical Physics},
number = 1,
volume = 147,
place = {United States},
year = {Fri Jul 07 00:00:00 EDT 2017},
month = {Fri Jul 07 00:00:00 EDT 2017}
}

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Cited by: 3 works
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Works referenced in this record:

Scalable molecular dynamics with NAMD
journal, January 2005

  • Phillips, James C.; Braun, Rosemary; Wang, Wei
  • Journal of Computational Chemistry, Vol. 26, Issue 16, p. 1781-1802
  • DOI: 10.1002/jcc.20289