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Title: Geometric Energy Derivatives at the Complete Basis Set Limit: Application to the Equilibrium Structure and Molecular Force Field of Formaldehyde

Journal Article · · Journal of Chemical Theory and Computation
ORCiD logo [1];  [2];  [3]; ORCiD logo [1];  [2];  [3];  [1]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ. of Georgia, Athens, GA (United States)
  2. Univ. of Texas at Austin, Austin, TX (United States)
  3. Univ. of Tromso - The Arctic Univ. of Norway, Tromso (Norway)
  4. Univ. of Florida, Gainesville, FL (United States)
+ Show Author Affiliations

Here, geometric energy derivatives which rely on core-corrected focal-point 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 fourth-order 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. Second-order 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 sum-over-states fourth-order vibrational perturbation theory (VPT4) formalism is employed herein, utilizing quintic and sextic derivatives obtained with a recursive algorithmic approach for response theory.

Research Organization:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0018412
OSTI ID:
1468297
Journal Information:
Journal of Chemical Theory and Computation, Vol. 14, Issue 3; ISSN 1549-9618
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Laboratory spectroscopic study of isotopic thioformaldehyde, H 2 CS, and determination of its equilibrium structure journal January 2019
Vibrational analysis of the ubiquitous interstellar molecule cyclopropenylidene ( c -C 3 H 2 ): the importance of numerical stability journal March 2019
Fourth-order vibrational perturbation theory with the Watson Hamiltonian: Report of working equations and preliminary results journal September 2018
State‐of‐the‐art computations of dipole moments using analytic gradients of high‐level density‐fitted coupled‐cluster methods with focal‐point approximations journal December 2019
Theoretical studies of atmospheric molecular complexes interacting with NIR to UV light journal January 2018
Astrophysical sulfur in diffuse and dark clouds: The fundamental vibrational frequencies and spectroscopic constants of hydrogen sulfide cation (H2S+) journal August 2018

Figures / Tables (11)

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