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Title: CC2 oscillator strengths within the local framework for calculating excitation energies (LoFEx)

Abstract

In a recent work [P. Baudin and K. Kristensen, J. Chem. Phys. 144, 224106 (2016)], we introduced a local framework for calculating excitation energies (LoFEx), based on second-order approximated coupled cluster (CC2) linear-response theory. LoFEx is a black-box method in which a reduced excitation orbital space (XOS) is optimized to provide coupled cluster (CC) excitation energies at a reduced computational cost. In this article, we present an extension of the LoFEx algorithm to the calculation of CC2 oscillator strengths. Two different strategies are suggested, in which the size of the XOS is determined based on the excitation energy or the oscillator strength of the targeted transitions. The two strategies are applied to a set of medium-sized organic molecules in order to assess both the accuracy and the computational cost of the methods. The results show that CC2 excitation energies and oscillator strengths can be calculated at a reduced computational cost, provided that the targeted transitions are local compared to the size of the molecule. Finally, to illustrate the potential of LoFEx for large molecules, both strategies have been successfully applied to the lowest transition of the bivalirudin molecule (4255 basis functions) and compared with time-dependent density functional theory.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Aarhus Univ., Aarhus (Denmark). qLEAP Center for Theoretical Chemistry, Dept. of Chemistry
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
European Union (EU); USDOE Office of Science (SC)
OSTI Identifier:
1565594
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 14; 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; Chemistry; Physics

Citation Formats

Baudin, Pablo, Kjærgaard, Thomas, and Kristensen, Kasper. CC2 oscillator strengths within the local framework for calculating excitation energies (LoFEx). United States: N. p., 2017. Web. doi:10.1063/1.4979713.
Baudin, Pablo, Kjærgaard, Thomas, & Kristensen, Kasper. CC2 oscillator strengths within the local framework for calculating excitation energies (LoFEx). United States. doi:10.1063/1.4979713.
Baudin, Pablo, Kjærgaard, Thomas, and Kristensen, Kasper. Fri . "CC2 oscillator strengths within the local framework for calculating excitation energies (LoFEx)". United States. doi:10.1063/1.4979713. https://www.osti.gov/servlets/purl/1565594.
@article{osti_1565594,
title = {CC2 oscillator strengths within the local framework for calculating excitation energies (LoFEx)},
author = {Baudin, Pablo and Kjærgaard, Thomas and Kristensen, Kasper},
abstractNote = {In a recent work [P. Baudin and K. Kristensen, J. Chem. Phys. 144, 224106 (2016)], we introduced a local framework for calculating excitation energies (LoFEx), based on second-order approximated coupled cluster (CC2) linear-response theory. LoFEx is a black-box method in which a reduced excitation orbital space (XOS) is optimized to provide coupled cluster (CC) excitation energies at a reduced computational cost. In this article, we present an extension of the LoFEx algorithm to the calculation of CC2 oscillator strengths. Two different strategies are suggested, in which the size of the XOS is determined based on the excitation energy or the oscillator strength of the targeted transitions. The two strategies are applied to a set of medium-sized organic molecules in order to assess both the accuracy and the computational cost of the methods. The results show that CC2 excitation energies and oscillator strengths can be calculated at a reduced computational cost, provided that the targeted transitions are local compared to the size of the molecule. Finally, to illustrate the potential of LoFEx for large molecules, both strategies have been successfully applied to the lowest transition of the bivalirudin molecule (4255 basis functions) and compared with time-dependent density functional theory.},
doi = {10.1063/1.4979713},
journal = {Journal of Chemical Physics},
number = 14,
volume = 146,
place = {United States},
year = {2017},
month = {4}
}

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