Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
Search:
   
 
 
 
Previous Article
Nature and location of excited charge-transfer states in porphyrin dimers: Development of preliminary design characteristics for biomimetic solar energy conversion systems
The ground and excited electronic states of a magnesium porphyrin–porphyrin (MgP–P) dimer in a variety of geometries have been investigated by ab initio configuration interaction calculati...
Next Article
Density functional theory of bound states of positrons in negative ions
Bound states of a single positron and a negative ion are studied in the self-interaction-corrected local spin density approximation (SIC-LSDA). The calculations do not include electron–electron ...

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

You are not logged in to this journal. Log in

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
BUY THIS ARTICLE   (US$24)
Download PDF (581 kB) View Cart

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)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. C. Y. Ng, in Advances in Chemical Physics, edited by I. Prigogine and S. A. Rice (Wiley, New York, 1983), Vol. 52, p. 263, and references therein.
  2. (a) N. C. Blais and E. A. Walters, J. Chem. Phys. 75, 4208 (1981);
    3. (b) 80, 3501 (1984);
    (c) H. F. Prest, W. B. Tzeng, J. M. Brom, and C. Y. Ng, J. Am. Chem. Soc. 105, 7531 (1983).
  3. (a) J. R. Sabin, J. Am. Chem. Soc. 93, 3613 (1971);
    4. (b) G. Leroy, G. Louterman-Leloup, and P. Ruelle, Bull. Soc. Chim. Belg. 85, 219 (1976);
    (c) K. Pecul, Theor. Chim. Acta 44, 77 (1977);
    (d) R. C. Kerns and L. C. Allen, J. Am. Chem. Soc. 100, 6587 (1978);
    (e) B. van Hensbergen, R. Block, and L. Jansen, J. Chem. Phys. 76, 3161 (1982).
  4. (a) S. Tomoda and K. Kimura, Chem. Phys. 82, 215 (1983);
    5. (b) Chem. Phys. Lett. 102, 560 (1983);
    (c) D. Moncrieff, I. H. Hillier, and V. R. Saunders, ibid. 89, 447 (1982);
    (d) S. Tomoda, Y. Achiba, and K. Kimura, ibid. 87, 197 (1982).
  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:
    6. W. J. Hehre, R. F. Stewart, and J. A. Pople, J. Chem. Phys. 51, 2657 (1969);
    W. J. Hehre, R. Ditchfield, R. F. Stewart, and J. A. Pople, ibid. 52, 2769 (1970).
    (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
    R. Bartlett, Annu. Rev. Phys. Chem. 32, 359 (1981).
  6. (a) M. M. Szczesniak and S. Scheiner, J. Chem. Phys. 80, 1535 (1984);
    7. (b) S. Scheiner, ibid. 78, 599 (1983);
    (c) Chem. Phys. Lett. 93, 540 (1982);
    (d) Z. Latajka and S. Scheiner, J. Chem. Phys. 81, 407 (1984);
    (e) L. A. Curtiss, D. J. Pochatko, A. E. Reed, and F. Weinhold, ibid. 82, 2679 (1985).

CITING ARTICLES
For access to citing articles, you need to log in.
For access to citing articles, you need to Log in.


Copyright © American Institute of Physics