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An exploration of electronic structure and nuclear dynamics in tropolone. I. The X-tilde   1A1 ground state

J. Chem. Phys. 124, 204307 (2006); doi:10.1063/1.2200343

Published 23 May 2006

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Lori A. Burns, Daniel Murdock, and Patrick H. Vaccaro
Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107
The ground electronic state (X-tilde   1A1) of tropolone has been examined theoretically by exploiting extensive sets of basis functions [e.g., 6-311++G(d,p) and aug-cc-pVDZ] in conjunction with the high levels of electron correlation made possible by density functional (DFT/B3LYP), Møller-Plesset perturbation (MP2), and coupled-cluster [CCSD and CCSD(T)] methods. Unconstrained MP2 and CCSD optimization procedures performed with the reference 6-311++G(d,p) basis predict a slightly nonplanar equilibrium structure characterized by a small barrier to skeletal inversion (<=10  cm–1 magnitude). Complementary harmonic frequency analyses have shown this nonplanarity to be a computational artifact arising from adversely tuned carbon d-orbital exponents embodied in the standard definitions of several Pople-type basis sets. Correlation-consistent bases such as Dunning's aug-cc-pVDZ are less susceptible to these effects and were employed to confirm that the X-tilde   1A1 hypersurface supports a rigorously planar global minimum. The fully optimized geometries and vibrational force fields obtained by applying potent coupled-cluster schemes to the relaxed-equilibrium (Cs) and transition-state (C2v) conformers of tropolone afford a trenchant glimpse of the key features that mediate intramolecular hydron exchange in this model system. By incorporating perturbative triples corrections at the substantial CCSD(T) level of theory, an interoxygen distance of rO[centered ellipsis]O=2.528  Å was determined for the minimum-energy configuration, with the accompanying proton-transfer reaction being hindered by a barrier of 2557.0  cm–1 height. The potential energy landscape in tropolone, as well as the nature of the attendant hydron migration process, is discussed within the framework of the encompassing G4 molecular symmetry group. ©2006 American Institute of Physics
History: Received 10 February 2006; accepted 4 April 2006; published 23 May 2006
Permalink: http://link.aip.org/link/?JCPSA6/124/204307/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Ew
    Density-functional theory (atoms and molecules)
  • 31.15.Md
    Perturbation theory (atoms and molecules)
  • 31.15.Dv
    Coupled cluster theory (atoms and molecules)
  • 33.20.Tp
    Vibrational analysis (molecular spectra)
  • 31.25.Eb
    Electron-correlation calculations for atoms and ions: ground state
  • 33.15.Bh
    General molecular conformation and symmetry; stereochemistry
  • YEAR: 2006

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0021-9606 (print)   1089-7690 (online)
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