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Title: Discontinuities-free complete-active-space state–specific multi–reference coupled cluster theory for describing bond stretching and dissociation

Abstract

The earlier proposed multi-reference state-specific coupled-cluster theory with the complete active space reference suffered from a problem of energy discontinuities when the formal reference state was changing in the calculation of the potential energy curve (PEC). A simple remedy to the discontinuity problem is found and is presented in this work. It involves using natural complete active space self-consistent field active orbitals in the complete active space coupled-cluster calculations. As a result, the approach gives smooth PECs for different types of dissociation problems, as illustrated in the calculations of the dissociation of the single bond in the hydrogen fluorine molecule and of the symmetric double-bond dissociation in the water molecule.

Authors:
 [1];  [1]; ORCiD logo [2];  [3]
+ Show Author Affiliations
  1. V. N. Karazin Kharkiv National Univ., Kharkiv (Ukraine)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); V. N. Karazin Kharkiv National Univ., Kharkiv (Ukraine)
  3. Univ. of Arizona, Tucson, AZ (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1439958
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 2; 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

Citation Formats

Zaporozhets, Irina A., Ivanov, Vladimir V., Lyakh, Dmitry I., and Adamowicz, Ludwik. Discontinuities-free complete-active-space state–specific multi–reference coupled cluster theory for describing bond stretching and dissociation. United States: N. p., 2015. Web. doi:10.1063/1.4926392.
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Zaporozhets, Irina A., Ivanov, Vladimir V., Lyakh, Dmitry I., & Adamowicz, Ludwik. Discontinuities-free complete-active-space state–specific multi–reference coupled cluster theory for describing bond stretching and dissociation. United States. https://doi.org/10.1063/1.4926392
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Zaporozhets, Irina A., Ivanov, Vladimir V., Lyakh, Dmitry I., and Adamowicz, Ludwik. Mon . "Discontinuities-free complete-active-space state–specific multi–reference coupled cluster theory for describing bond stretching and dissociation". United States. https://doi.org/10.1063/1.4926392. https://www.osti.gov/servlets/purl/1439958.
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@article{osti_1439958,
title = {Discontinuities-free complete-active-space state–specific multi–reference coupled cluster theory for describing bond stretching and dissociation},
author = {Zaporozhets, Irina A. and Ivanov, Vladimir V. and Lyakh, Dmitry I. and Adamowicz, Ludwik},
abstractNote = {The earlier proposed multi-reference state-specific coupled-cluster theory with the complete active space reference suffered from a problem of energy discontinuities when the formal reference state was changing in the calculation of the potential energy curve (PEC). A simple remedy to the discontinuity problem is found and is presented in this work. It involves using natural complete active space self-consistent field active orbitals in the complete active space coupled-cluster calculations. As a result, the approach gives smooth PECs for different types of dissociation problems, as illustrated in the calculations of the dissociation of the single bond in the hydrogen fluorine molecule and of the symmetric double-bond dissociation in the water molecule.},
doi = {10.1063/1.4926392},
journal = {Journal of Chemical Physics},
number = 2,
volume = 143,
place = {United States},
year = {Mon Jul 13 00:00:00 EDT 2015},
month = {Mon Jul 13 00:00:00 EDT 2015}
}
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https://doi.org/10.1063/1.4926392
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Cited by: 6 works
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Figures / Tables:

FIG. 1 FIG. 1: Absolute values of the configuration coefficients in the wave functions of the LiH molecule obtained in the CASSCF(2,2)/TZV calculations.
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    Works referencing / citing this record:

    Partially linearized external models to active-space coupled-cluster through connected hextuple excitations
    journal, January 2018

    • Xu, Enhua; Ten-no, Seiichiro L.
    • Journal of Computational Chemistry, Vol. 39, Issue 15
    • DOI: 10.1002/jcc.25163

    A simplified account of the correlation effects to bond breaking processes: The Brillouin-Wigner perturbation theory using a multireference formulation
    journal, August 2019

    • Manna, Shovan; Ray, Suvonil Sinha; Chattopadhyay, Sudip
    • The Journal of Chemical Physics, Vol. 151, Issue 6
    • DOI: 10.1063/1.5097657
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      TABLE III (p. 9)table
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