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Title: A local framework for calculating coupled cluster singles and doubles excitation energies (LoFEx-CCSD)

Here, the recently developed Local Framework for calculating Excitation energies (LoFEx) is extended to the coupled cluster singles and doubles (CCSD) model. In the new scheme, a standard CCSD excitation energy calculation is carried out within a reduced excitation orbital space (XOS), which is composed of localised molecular orbitals and natural transition orbitals determined from time-dependent Hartree–Fock theory. The presented algorithm uses a series of reduced second-order approximate coupled cluster singles and doubles (CC2) calculations to optimise the XOS in a black-box manner. This ensures that the requested CCSD excitation energies have been determined to a predefined accuracy compared to a conventional CCSD calculation. We present numerical LoFEx-CCSD results for a set of medium-sized organic molecules, which illustrate the black-box nature of the approach and the computational savings obtained for transitions that are local compared to the size of the molecule. In fact, for such local transitions, the LoFEx-CCSD scheme can be applied to molecular systems where a conventional CCSD implementation is intractable.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [1]
  1. Aarhus Univ., Aarhus (Denmark)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Molecular Physics
Additional Journal Information:
Journal Volume: 115; Journal Issue: 17-18; Journal ID: ISSN 0026-8976
Publisher:
Taylor & Francis
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; excitation energies; large molecules; coupled cluster theory; CCSD; local correlation
OSTI Identifier:
1345012

Baudin, Pablo, Bykov, Dmytro, Liakh, Dmitry I., Ettenhuber, Patrick, and Kristensen, Kasper. A local framework for calculating coupled cluster singles and doubles excitation energies (LoFEx-CCSD). United States: N. p., Web. doi:10.1080/00268976.2017.1290836.
Baudin, Pablo, Bykov, Dmytro, Liakh, Dmitry I., Ettenhuber, Patrick, & Kristensen, Kasper. A local framework for calculating coupled cluster singles and doubles excitation energies (LoFEx-CCSD). United States. doi:10.1080/00268976.2017.1290836.
Baudin, Pablo, Bykov, Dmytro, Liakh, Dmitry I., Ettenhuber, Patrick, and Kristensen, Kasper. 2017. "A local framework for calculating coupled cluster singles and doubles excitation energies (LoFEx-CCSD)". United States. doi:10.1080/00268976.2017.1290836. https://www.osti.gov/servlets/purl/1345012.
@article{osti_1345012,
title = {A local framework for calculating coupled cluster singles and doubles excitation energies (LoFEx-CCSD)},
author = {Baudin, Pablo and Bykov, Dmytro and Liakh, Dmitry I. and Ettenhuber, Patrick and Kristensen, Kasper},
abstractNote = {Here, the recently developed Local Framework for calculating Excitation energies (LoFEx) is extended to the coupled cluster singles and doubles (CCSD) model. In the new scheme, a standard CCSD excitation energy calculation is carried out within a reduced excitation orbital space (XOS), which is composed of localised molecular orbitals and natural transition orbitals determined from time-dependent Hartree–Fock theory. The presented algorithm uses a series of reduced second-order approximate coupled cluster singles and doubles (CC2) calculations to optimise the XOS in a black-box manner. This ensures that the requested CCSD excitation energies have been determined to a predefined accuracy compared to a conventional CCSD calculation. We present numerical LoFEx-CCSD results for a set of medium-sized organic molecules, which illustrate the black-box nature of the approach and the computational savings obtained for transitions that are local compared to the size of the molecule. In fact, for such local transitions, the LoFEx-CCSD scheme can be applied to molecular systems where a conventional CCSD implementation is intractable.},
doi = {10.1080/00268976.2017.1290836},
journal = {Molecular Physics},
number = 17-18,
volume = 115,
place = {United States},
year = {2017},
month = {2}
}