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A coupled cluster study of As2

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

Issue Date: 1 June 1990

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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
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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

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (30)
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  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).

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