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  A case study of density functional theory and domain-based local pair natural orbital coupled cluster for vibrational effects on EPR hyperfine coupling constants: vibrational perturbation theory versus ab initio molecular dynamics

Auer, A. A., Tran, V. A., Sharma, B., Stoychev, G. L., Marx, D., & Neese, F. (2020). A case study of density functional theory and domain-based local pair natural orbital coupled cluster for vibrational effects on EPR hyperfine coupling constants: vibrational perturbation theory versus ab initio molecular dynamics. Molecular Physics, 118(19-20): e1797916. doi:10.1080/00268976.2020.1797916.

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 Creators:
Auer, Alexander A.1, Author              
Tran, Van Anh2, Author              
Sharma, Bikramjit3, Author
Stoychev, Georgi L.1, Author              
Marx, Dominik3, Author
Neese, Frank2, Author              
Affiliations:
1Research Group Auer, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541705              
2Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              
3Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, Bochum, Germany, ou_persistent22              

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Free keywords: Electron paramagnetic resonance; hyperfine coupling constants; ab initio calculations; vibrational corrections; ab initio molecular dynamics
 Abstract: Local approximations of high-level ab initio methods make superior accuracy in the computation of molecular properties accessible by drastically decreasing computational times. As a consequence, these methods become applicable not only for large systems but also in schemes for which large numbers of calculations are necessary. In this work, we apply a recently developed open-shell implementation of the domain-based pair natural orbital coupled cluster singles doubles (DLPNO-CCSD) approach for the computation of vibrational corrections to the isotropic values of electron paramagnetic resonance (EPR) hyperfine coupling constants. We assess density functional theory (DFT) and DLPNO-CCSD approaches using two common but very different schemes: (1) vibrational perturbation theory based on equilibrium geometries, and (2) explicit canonical ensemble averages using configuration snapshots sampled from revPBE0-D3(0) ab initio molecular dynamics simulations. Both approaches are found to yield very similar results for the spin probe 2,2,3,4,5,5-hexamethylperhydroimidazol-1-oxyl (HMI) and are both feasible for systems of around 30 atoms. However, the numerical stability required for higher derivatives can become a limitation for local correlation methods in the case of vibrational perturbation theory.

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Language(s): eng - English
 Dates: 2020-04-142020-07-072020-07-312020-10-01
 Publication Status: Published in print
 Pages: 16
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1080/00268976.2020.1797916
 Degree: -

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Title: Molecular Physics
  Other : Mol. Phys.
Source Genre: Journal
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Publ. Info: London : Taylor & Francis
Pages: - Volume / Issue: 118 (19-20) Sequence Number: e1797916 Start / End Page: - Identifier: ISSN: 0026-8976
CoNE: https://pure.mpg.de/cone/journals/resource/954925264211