Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory
A nearly linear scaling implementation of coupled-cluster with singles and doubles excitations (CCSD) can be achieved by means of the domain-based local pair natural orbital (DLPNO) method. The combination of DLPNO-CCSD with implicit solvation methods allows the calculation of accurate energies and...
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ftpubman:oai:pure.mpg.de:item_3335953 2023-08-27T04:11:26+02:00 Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory Garcia-Ratés, M. Becker, U. Neese, F. 2021-10-15 http://hdl.handle.net/21.11116/0000-0009-40F4-B eng eng info:eu-repo/semantics/altIdentifier/doi/10.1002/jcc.26726 http://hdl.handle.net/21.11116/0000-0009-40F4-B Journal of Computational Chemistry info:eu-repo/semantics/article 2021 ftpubman https://doi.org/10.1002/jcc.26726 2023-08-02T00:46:57Z A nearly linear scaling implementation of coupled-cluster with singles and doubles excitations (CCSD) can be achieved by means of the domain-based local pair natural orbital (DLPNO) method. The combination of DLPNO-CCSD with implicit solvation methods allows the calculation of accurate energies and chemical properties of solvated systems at an affordable computational cost. We have efficiently implemented different schemes within the conductor-like polarizable continuum model (C-PCM) for DLPNO-CCSD in the ORCA quantum chemistry suite. In our implementation, the overhead due to the additional solvent terms amounts to less than 5% of the time the equivalent gas phase job takes. Our results for organic neutrals and open-shell ions in water show that for most systems, adding solvation terms to the coupled-cluster amplitudes equations and to the energy leads to small changes in the total energy compared to only considering solvated orbitals and corrections to the reference energy. However, when the solute contains certain functional groups, such as carbonyl or nitrile groups, the changes in the energy are larger and estimated to be around 0.04 and 0.02 kcal/mol for each carbonyl and nitrile group in the solute, respectively. For solutes containing metals, the use of accurate CC/C-PCM schemes is crucial to account for correlation solvation effects. Simultaneously, we have calculated the electrostatic component of the solvation energy for neutrals and ions in water for the different DLPNO-CCSD/C-PCM schemes. We observe negligible changes in the deviation between DLPNO-CCSD and canonical-CCSD data. Here, DLPNO-CCSD results outperform those for Hartree-Fock and density functional theory calculations. Article in Journal/Newspaper Orca Max Planck Society: MPG.PuRe Hartree ENVELOPE(-44.716,-44.716,-60.783,-60.783) Journal of Computational Chemistry 42 27 1959 1973 |
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Max Planck Society: MPG.PuRe |
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ftpubman |
language |
English |
description |
A nearly linear scaling implementation of coupled-cluster with singles and doubles excitations (CCSD) can be achieved by means of the domain-based local pair natural orbital (DLPNO) method. The combination of DLPNO-CCSD with implicit solvation methods allows the calculation of accurate energies and chemical properties of solvated systems at an affordable computational cost. We have efficiently implemented different schemes within the conductor-like polarizable continuum model (C-PCM) for DLPNO-CCSD in the ORCA quantum chemistry suite. In our implementation, the overhead due to the additional solvent terms amounts to less than 5% of the time the equivalent gas phase job takes. Our results for organic neutrals and open-shell ions in water show that for most systems, adding solvation terms to the coupled-cluster amplitudes equations and to the energy leads to small changes in the total energy compared to only considering solvated orbitals and corrections to the reference energy. However, when the solute contains certain functional groups, such as carbonyl or nitrile groups, the changes in the energy are larger and estimated to be around 0.04 and 0.02 kcal/mol for each carbonyl and nitrile group in the solute, respectively. For solutes containing metals, the use of accurate CC/C-PCM schemes is crucial to account for correlation solvation effects. Simultaneously, we have calculated the electrostatic component of the solvation energy for neutrals and ions in water for the different DLPNO-CCSD/C-PCM schemes. We observe negligible changes in the deviation between DLPNO-CCSD and canonical-CCSD data. Here, DLPNO-CCSD results outperform those for Hartree-Fock and density functional theory calculations. |
format |
Article in Journal/Newspaper |
author |
Garcia-Ratés, M. Becker, U. Neese, F. |
spellingShingle |
Garcia-Ratés, M. Becker, U. Neese, F. Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory |
author_facet |
Garcia-Ratés, M. Becker, U. Neese, F. |
author_sort |
Garcia-Ratés, M. |
title |
Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory |
title_short |
Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory |
title_full |
Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory |
title_fullStr |
Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory |
title_full_unstemmed |
Implicit solvation in domain based pair natural orbital coupled cluster (DLPNO-CCSD) theory |
title_sort |
implicit solvation in domain based pair natural orbital coupled cluster (dlpno-ccsd) theory |
publishDate |
2021 |
url |
http://hdl.handle.net/21.11116/0000-0009-40F4-B |
long_lat |
ENVELOPE(-44.716,-44.716,-60.783,-60.783) |
geographic |
Hartree |
geographic_facet |
Hartree |
genre |
Orca |
genre_facet |
Orca |
op_source |
Journal of Computational Chemistry |
op_relation |
info:eu-repo/semantics/altIdentifier/doi/10.1002/jcc.26726 http://hdl.handle.net/21.11116/0000-0009-40F4-B |
op_doi |
https://doi.org/10.1002/jcc.26726 |
container_title |
Journal of Computational Chemistry |
container_volume |
42 |
container_issue |
27 |
container_start_page |
1959 |
op_container_end_page |
1973 |
_version_ |
1775354219996381184 |