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Overcoming the Failure of Correlation for Out-of-Plane Motions in a Simple Aromatic: Rovibrational Quantum Chemical Analysis of c-C3H2

  • Ryan C. Fortenberry*
    Ryan C. Fortenberry
    Georgia Southern University, Department of Chemistry & Biochemistry, Statesboro, Georgia 30460, United States
    *E-mail: [email protected]. Phone: 912-478-7694.
  • Carlie M. Novak
    Carlie M. Novak
    Georgia Southern University, Department of Chemistry & Biochemistry, Statesboro, Georgia 30460, United States
  • Joshua P. Layfield
    Joshua P. Layfield
    University of St. Thomas, Department of Chemsitry, St. Paul, Minnesota 55105, United States
  • Eduard Matito
    Eduard Matito
    Kimika Fakultatea, Euskal Herriko Unibertsitatea, UPV/EHU, and Donostia International Physics Center (DIPC), P.K. 1072, 20080 Donostia, Euskadi, Spain
    Ikerbasque, Basque Foundation for Science, 48013 Bilbao, Spain
  • , and 
  • Timothy J. Lee
    Timothy J. Lee
    MS 245-3 NASA Ames Research Center, Moffett Field, California 94035-1000, United States
Cite this: J. Chem. Theory Comput. 2018, 14, 4, 2155–2164
Publication Date (Web):March 9, 2018
https://doi.org/10.1021/acs.jctc.8b00164
Copyright © 2018 American Chemical Society

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    Abstract

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    Truncated, correlated, wave function methods either produce imaginary frequencies (in the extreme case) or nonphysically low frequencies in out-of-plane motions for carbon and adjacent atoms when the carbon atoms engage in π bonding. Cyclopropenylidene is viewed as the simplest aromatic hydrocarbon, and the present as well as previous theoretical studies have shown that this simple molecule exhibits this behavior in the two out-of-plane bends (OPBs). This nonphysical behavior has been treated by removing nearly linear dependent basis functions according to eigenvalues of the overlap matrix, by employing basis sets where the spd space saturatation is balanced with higher angular momentum functions, by including basis set superposition/incompleteness error (BSSE/BSIE) corrections, or by combining standard correlation methods with explicitly correlated methods to produce hybrid potential surfaces. However, this work supports the recently described hypothesis that the OPB problem is both a method and a basis set effect. The correlated wave function’s largest higher-order substitution term comes from a π → π* excitation where constructive interference of both orbitals artificially stabilizes the OPB. By employing schema to overcome this issue, the symmetric OPB ν9 is the predicted to be the second-brightest transition, and it will be observed very close to 775 cm–1. However, more work from the community is required to formulate better how carbon atoms interact with their adjacent atoms in π-bonded systems. Such bonds are ubiquitous in all of chemistry and beyond.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jctc.8b00164.

    • Tables for the CcCR cubic and quartic force constants as well as the vibrational frequencies and rotational constants for c-C3H2 determined from each of the scaled, trial force constants (PDF)

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