Geometric Energy Derivatives at the Complete Basis Set Limit: Application to the Equilibrium Structure and Molecular Force Field of Formaldehyde
Abstract
Here, geometric energy derivatives which rely on corecorrected focalpoint energies extrapolated to the complete basis set (CBS) limit of coupled cluster theory with iterative and noniterative quadruple excitations, CCSDTQ and CCSDT(Q), are used as elements of molecular gradients and, in the case of CCSDT(Q), expansion coefficients of an anharmonic force field. These gradients are used to determine the CCSDTQ/CBS and CCSDT(Q)/CBS equilibrium structure of the S_{0} ground state of H_{2}CO where excellent agreement is observed with previous work and experimentally derived results. A fourthorder expansion about this CCSDT(Q)/CBS reference geometry using the same level of theory produces an exceptional level of agreement to spectroscopically observed vibrational band origins with a MAE of 0.57 cm^{–1}. Secondorder vibrational perturbation theory (VPT2) and variational discrete variable representation (DVR) results are contrasted and discussed. Vibration–rotation, anharmonicity, and centrifugal distortion constants from the VPT2 analysis are reported and compared to previous work. Additionally, an initial application of a sumoverstates fourthorder vibrational perturbation theory (VPT4) formalism is employed herein, utilizing quintic and sextic derivatives obtained with a recursive algorithmic approach for response theory.
 Authors:

 Univ. of Georgia, Athens, GA (United States)
 Univ. of Texas at Austin, Austin, TX (United States)
 Univ. of Tromso  The Arctic Univ. of Norway, Tromso (Norway)
 Univ. of Florida, Gainesville, FL (United States)
 Publication Date:
 Research Org.:
 Univ. of Georgia, Athens, GA (United States)
 Sponsoring Org.:
 USDOE Office of Science (SC), Basic Energy Sciences (BES)
 OSTI Identifier:
 1468297
 Grant/Contract Number:
 SC0018412
 Resource Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Theory and Computation
 Additional Journal Information:
 Journal Volume: 14; Journal Issue: 3; Journal ID: ISSN 15499618
 Publisher:
 American Chemical Society
 Country of Publication:
 United States
 Language:
 English
 Subject:
 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
Citation Formats
Morgan, W. James, Matthews, Devin A., Ringholm, Magnus, Agarwal, Jay, Gong, Justin Z., Ruud, Kenneth, Allen, Wesley D., Stanton, John F., and Schaefer, III, Henry F. Geometric Energy Derivatives at the Complete Basis Set Limit: Application to the Equilibrium Structure and Molecular Force Field of Formaldehyde. United States: N. p., 2018.
Web. doi:10.1021/acs.jctc.7b01138.
Morgan, W. James, Matthews, Devin A., Ringholm, Magnus, Agarwal, Jay, Gong, Justin Z., Ruud, Kenneth, Allen, Wesley D., Stanton, John F., & Schaefer, III, Henry F. Geometric Energy Derivatives at the Complete Basis Set Limit: Application to the Equilibrium Structure and Molecular Force Field of Formaldehyde. United States. doi:10.1021/acs.jctc.7b01138.
Morgan, W. James, Matthews, Devin A., Ringholm, Magnus, Agarwal, Jay, Gong, Justin Z., Ruud, Kenneth, Allen, Wesley D., Stanton, John F., and Schaefer, III, Henry F. Fri .
"Geometric Energy Derivatives at the Complete Basis Set Limit: Application to the Equilibrium Structure and Molecular Force Field of Formaldehyde". United States. doi:10.1021/acs.jctc.7b01138. https://www.osti.gov/servlets/purl/1468297.
@article{osti_1468297,
title = {Geometric Energy Derivatives at the Complete Basis Set Limit: Application to the Equilibrium Structure and Molecular Force Field of Formaldehyde},
author = {Morgan, W. James and Matthews, Devin A. and Ringholm, Magnus and Agarwal, Jay and Gong, Justin Z. and Ruud, Kenneth and Allen, Wesley D. and Stanton, John F. and Schaefer, III, Henry F.},
abstractNote = {Here, geometric energy derivatives which rely on corecorrected focalpoint energies extrapolated to the complete basis set (CBS) limit of coupled cluster theory with iterative and noniterative quadruple excitations, CCSDTQ and CCSDT(Q), are used as elements of molecular gradients and, in the case of CCSDT(Q), expansion coefficients of an anharmonic force field. These gradients are used to determine the CCSDTQ/CBS and CCSDT(Q)/CBS equilibrium structure of the S0 ground state of H2CO where excellent agreement is observed with previous work and experimentally derived results. A fourthorder expansion about this CCSDT(Q)/CBS reference geometry using the same level of theory produces an exceptional level of agreement to spectroscopically observed vibrational band origins with a MAE of 0.57 cm–1. Secondorder vibrational perturbation theory (VPT2) and variational discrete variable representation (DVR) results are contrasted and discussed. Vibration–rotation, anharmonicity, and centrifugal distortion constants from the VPT2 analysis are reported and compared to previous work. Additionally, an initial application of a sumoverstates fourthorder vibrational perturbation theory (VPT4) formalism is employed herein, utilizing quintic and sextic derivatives obtained with a recursive algorithmic approach for response theory.},
doi = {10.1021/acs.jctc.7b01138},
journal = {Journal of Chemical Theory and Computation},
number = 3,
volume = 14,
place = {United States},
year = {2018},
month = {2}
}
Web of Science
Figures / Tables:
Works referencing / citing this record:
Laboratory spectroscopic study of isotopic thioformaldehyde, H _{2} CS, and determination of its equilibrium structure
journal, January 2019
 Müller, Holger S. P.; Maeda, Atsuko; Thorwirth, Sven
 Astronomy & Astrophysics, Vol. 621
Theoretical studies of atmospheric molecular complexes interacting with NIR to UV light
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 Biczysko, Malgorzata; Krupa, Justyna; Wierzejewska, Maria
 Faraday Discussions, Vol. 212
Theoretical studies of atmospheric molecular complexes interacting with NIR to UV light
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 Biczysko, Malgorzata; Krupa, Justyna; Wierzejewska, Maria
 Faraday Discussions, Vol. 212
Laboratory spectroscopic study of isotopic thioformaldehyde, H _{2} CS, and determination of its equilibrium structure
journal, January 2019
 Müller, Holger S. P.; Maeda, Atsuko; Thorwirth, Sven
 Astronomy & Astrophysics, Vol. 621
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 Morgan, W. James; Fortenberry, Ryan C.; Schaefer III, Henry F.
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 Monthly Notices of the Royal Astronomical Society, Vol. 480, Issue 3