Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
Structure of phosphorus clusters using simulated annealing—P2 to P8
The geometries of low-lying isomers of phosphorus clusters P2 to P8 have been calculated using a density functional (DF) method, combined with molecular dynamics (MD) and simulated annealing technique...
Next Article
Ground and excited states of CaCH3, CaNH2, CaOH, and CaF through electron propagator calculations
Ground and excited state energies of CaCH3, CaNH2, CaOH, and CaF are obtained from electron propagator calculations of electron affinities of the corresponding cations at the optimized geometries of t...

A coupled cluster study of As2

J. Chem. Phys. 92, 6722 (1990); doi:10.1063/1.458307

Issue Date: 1 June 1990

You are not logged in to this journal. Log in

Gustavo E. Scuseria
Department of Chemistry and Rice Quantum Institute, Rice University, P. O. Box 1892, Houston, Texas 77251
Theoretical calculations at the self-consistent field (SCF) and coupled-cluster method including all single and double excitations (CCSD) have been carried out for As2. A variety of basis sets employing both segmented contractions and atomic natural orbitals have been developed and investigated. The predicted equilibrium bond length (re=2.107 Å), harmonic vibrational frequency (omegae=447 cm−1), and ionization potentials (9.75, 10.08, and 14.78 eV) are in excellent agreement with experimental values 2.103 Å, 430 cm−1, and 9.89 eV, 10.22 eV, and 15.32 eV; respectively. The best theoretical estimates for the dissociation energy (71.6 kcal/mol) and for the electron affinity (0.56 eV) were obtained at the CCSD level of theory employing large basis sets. However, given the importance of correlation effects on these two properties (the corresponding SCF values are 12.4 kcal/mol and 0.42 eV), the theoretical predictions could substantially be affected by the inclusion of connected triple excitations not considered in this work. The open-shell atomic As(4S) and diatomic calculations for As<sup> + </sup><sub>2</sub> and As<sup> - </sup><sub>2</sub> were carried out using a recently developed CCSD program that is based on restricted Hartree–Fock references and does not include any spin contamination for the correlation energies. The importance of correlating 3d electrons and the basis-set superposition error for De are analyzed. The effect of including d- and f-type polarization functions in the basis set is also discussed. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 31 January 1990; accepted 8 March 1990
Permalink: http://link.aip.org/link/?JCPSA6/92/6722/1
BUY THIS ARTICLE   (US$28)
Download PDF (654 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 36.40.+d
    Studies of special atoms and molecules Atomic and molecular clusters
  • 31.20.Ej
    Electronic structure of atoms and molecules: theory Specific calculations and results Ab initio MO calculations
  • 35.20.Vf
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Ionization potentials, electron affinities, molecular core binding energy
  • 35.20.Dp
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Interatomic distances and angles
  • YEAR: 1990

RELATED DATABASES


To view database links for this article,
you need to log in.
To view database links for this article,
you need to log in.

PUBLICATION DATA

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

REFERENCES (30)
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. Y. Liu, Q. Zhang, F. K. Tittel, R. F. Curl, and R. E. Smalley, J. Chem. Phys. 85, 7434 (1986).
  2. Q. Zhang, Y. Liu, R. F. Curl, F. K. Tittle and R. E. Smalley, J. Chem. Phys. 88, 1670 (1988).
  3. M. L. Mandich, W. D. Reents, and V. E. Bondybey, Atomic and Molecular Clusters, edited by E. R. Bernstein (Elsevier, New York, 1989).
  4. K. P. Huber and G. Herzberg, Constants of Diatomic Molecules (Van Nostrand, New York, 1979).
  5. S. L. Bennett, J. L. Margrave, J. L. Franklim, and J. E. Hudson, J. Chem. Phys. 59, 5814 (1973).
  6. J. M. Dyke, S. Elber, A. Morris, and J. C. H. Stevens, J. Chem. Soc. Faraday Trans. 2 82, 637 (1986);
    7. S. Ebel, H. Dieck, and H. Walter, Inorg. Chim. Acta 53, 1101 (1981).
  7. G. Trinquier, J. P. Malrieu, and J. P. Daudey, Chem. Phys. Lett. 80, 552 (1981).
  8. R. Kok and M. B. Hall, Inorg. Chem. 22, 728 (1983).
  9. Y. Watanabe, Y. Sakai, and H. Kashiwagi, Chem. Phys. Lett. 120, 363 (1985).
  10. S. Huzinaga, L. Seijo, Z. Barandiarán, and M. Klobukowski, J. Chem. Phys. 86, 2132 (1987).
  11. K. Balasubramanian, J. Mol. Spectrosc. 121, 465 (1987).
  12. J. Andzelm, N. Russo, and D. Salahub, Chem. Phys. Lett. 142, 169 (1987).
  13. T. H. Dunning, J. Chem. Phys. 66, 1382 (1977).
  14. R. S. Grev (private communication).
  15. J. Almlöf and P. R. Taylor, J. Chem. Phys. 86, 4070 (1987).
  16. H. Partridge, J. Chem. Phys. 90, 1043 (1989).
  17. G. D. Purvis and R. J. Bartlett, J. Chem. Phys. 76, 1910 (1982).
  18. G. E. Scuseria, A. C. Scheiner, T. J. Lee, J. E. Rice, and H. F. Schaefer, J. Chem. Phys. 86, 2881 (1987).
  19. G. E. Scuseria, C. L. Janssen, and H. F. Schaefer, J. Chem. Phys. 89, 7382 (1988).
  20. T. J. Lee and J. E. Rice, Chem. Phys. Lett. 150, 406 (1988).
  21. P. Pulay, in Applications of Electronic Structure Theory, edited by H. F. Schaefer (Plenum, New York, 1977).
  22. A. C. Scheiner, G. E. Scuseria, J. E. Rice, T. J. Lee, and H. F. Schaefer, J. Chem. Phys. 87, 5361 (1987).
  23. G. E. Scuseria (unpublished).
  24. R. Ahlrichs, M. Bär, M. Häser, H. Horn, and C. Kolmel, Chem. Phys. Lett. 162, 165 (1989).
  25. P. Saxe, D. J. Fox, H. F. Schaefer, and N. C. Hardy, J. Chem. Phys. 77, 5584 (1982).
  26. E. R. Davidson, in The World of Quantum Chemistry, edited by R. Daudel and B. Pullman (Reidel, Dordrecht, 1974), pp. 17–30.
  27. A. C. Scheiner, G. E. Scuseria, and H. F. Schaefer, J. Am. Chem. Soc. 108, 8160 (1986).
  28. G. E. Scuseria and H. F. Schaefer, J. Am. Chem. Soc. 111, 7761 (1989).
  29. G. E. Scuseria and H. F. Schaefer, J. Phys. Chem. (in press).
  30. J. Almlöf, B. J. DeLeeuw, P. R. Taylor, C. W. Bauschlicher, and P. Siegbahn, Int. J. Quantum Chem. Symp. 23, 345 (1989).

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