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Calculations on species relevant to the photoionization of the van der Waals molecule (H2S)2

J. Chem. Phys. 84, 1653 (1986); doi:10.1063/1.450460

Issue Date: 1 February 1986

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Pelayo F. Fernández, J. V. Ortiz, and Edward A. Walters
Department of Chemistry, University of New Mexico, Albuquerque, New Mexico 87131
Ab initio geometry optimizations are performed on the neutral and cation of H2S and (H2S)2. The neutral dimer is a weakly bound complex possessing only shallow minima in the potential energy surface, but the dimer cation has a deeper minimum where a proton has been transferred to give a complex of H3S+ and HS. Dimer binding energies, ionization energies, and appearance potentials are calculated. Intermonomer distances can be quite sensitive to basis set and correlation improvements on the HF/6-31G* level of theory. The potential energy surfaces, however, are flat enough so that the energetic consequences are not large. A simple procedure for estimating energy changes involving ionization is suggested; this method separates an adiabatic energy difference into a vertical ionization followed by a geometric relaxation. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 30 August 1985; accepted 14 October 1985
Permalink: http://link.aip.org/link/?JCPSA6/84/1653/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.80.Eh
    Molecular spectra and interactions of molecules with photons Photon interactions with molecules Autoionization, photoionization, and photodetachment
  • 35.20.Gs
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Bond strengths, dissociation energies, hydrogen bonding, etc.
  • YEAR: 1986

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (6)
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  5. Calculations performed with GAUSSIAN-82, Release A by J. S. Binkley, D. DeFrees, M. Frisch, E. Fluder, J. A. Pople, K. Ragavachari, H. B. Schlegel, R. Seeger, and R. Whiteside, Carnegie-Mellon University, Pittsburgh, PA. (a) STO-3G:
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    (b) 3-21G and 3-21G*:J. S. Binkley, J. A. Pople, and W. J. Hehre, J. Am. Chem. Soc. 102, 939 (1980);
    M. S. Gordon, J. S. Binkley, J. A. Pople, W. J. Pietro, and W. J. Hehre, ibid. 104, 2797 (1982);
    W. J. Pietro, M. M. Francl, W. J. Hehre, D. J. DeFrees, J. A. Pople, and J. S. Binkley, ibid. 104, 5039 (1982).
    (c) 6-31G and 6-31G*:W. J. Hehre, R. Ditchfield, and J. A. Pople, J. Chem. Phys. 56, 2257 (1972);
    M. M. Francl, W. J. Pietro, W. J. Hehre, J. S. Binkley, M. S. Gordon, D. J. DeFrees, and J. A. Pople, ibid. 77, 3654 (1982).
    (d) The extra d function is a single Gaussian with exponent = 0.023. This value was energy optimized for (H2S)2 at the optimum HF/6-31G* linear geometry. (e) For a review of correlation corrections to total energies via many-body perturbation theory employing the Møller-Plesset partitioning of the electronic Hamiltonian see
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    (e) L. A. Curtiss, D. J. Pochatko, A. E. Reed, and F. Weinhold, ibid. 82, 2679 (1985).

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