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Ab initio molecular orbital calculations on HBr<sup> - </sup><sub>2</sub> Geometry, frequencies, and enthalpy changes
HBr - 2" align="middle"/> has Dh symmetry at both the second-order (MP2) and third-order (MP3) Møller–Plesset perturbation levels of theory with the extended basis sets, whereas the Hartr...
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Gaussian-1 theory of molecular energies for second-row compounds

J. Chem. Phys. 93, 2537 (1990); doi:10.1063/1.458892

Issue Date: 15 August 1990

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Larry A. Curtiss and Christopher Jones
Chemical Technology Division/Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439

Gary W. Trucks and Krishnan Raghavachari
AT&T Bell Laboratories, Murray Hill, New Jersey 07974

John A. Pople
Department of Chemistry, Carnegie-Mellon University, Pittsburgh, Pennsylvania 15213
The Gaussian-1 theoretical procedure is extended and tested on compounds containing second-row atoms (Na–Cl). This is a composite procedure based on ab initio molecular orbital theory, utilizing large basis sets (including diffuse-sp, double-d, and f-polarization functions) and treating electron correlation by Møller–Plesset perturbation theory and by quadratic configuration interaction. Total atomization energies for a set of 24 species agree with accurate experimental data to an accuracy of better than 3 kcal/mol in most cases, SO2 being the notable exception. Similar agreement is achieved for ionization energies, electron affinities, and proton affinities. The method is used to assess experimental data for a number of other compounds having less accurate atomization energies. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 27 March 1990; accepted 24 May 1990
Permalink: http://link.aip.org/link/?JCPSA6/93/2537/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.20.Ej
    Electronic structure of atoms and molecules: theory Specific calculations and results Ab initio MO calculations
  • 31.20.Tz
    Electronic structure of atoms and molecules: theory Specific calculations and results Electron correlation and CI calculations
  • 35.20.Gs
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Bond strengths, dissociation energies, hydrogen bonding, etc.
  • 35.20.Vf
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Ionization potentials, electron affinities, molecular core binding energy
  • YEAR: 1990

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (31)
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  1. J. A. Pople, M. Head-Gordon, D. J. Fox, K. Raghavachari, and L. A. Curtiss, J. Chem. Phys. 90, 5622 (1989).
  2. L. A. Curtiss and J. A. Pople, J. Chem. Phys. 88, 7405 (1988);
    3. 90, 4314 (1989);
    91, 5118 (1989).
  3. K. Raghavachari, G. W. Trucks, J. A. Pople, and E. Replogle, Chem. Phys. Lett. 158, 207 (1989).
  4. (a) J. A. Pople, B. T. Luke, M. J. Frisch, and J. S. Binkley, J. Phys. Chem. 89, 2198 (1985);
    5. (b) J. A. Pople and L. A. Curtiss, ibid. 91, 155 (1987).
  5. J. A. Pople, M. Head-Gordon, and K. Raghavachari, J. Chem. Phys. 87, 5968 (1987).
  6. A. D. McLean and G. S. Chandler, J. Chem. Phys. 72, 5639 (1980).
  7. J. Heitzinger and M. S. Gordon, J. Phys. Chem. 91, 2353 (1987).
  8. P. C. Hariharan and J. A. Pople, Theor. Chim. Acta 28, 213 (1973).
  9. M. J. Frisch, M. Head-Gordon, H. B. Schlegel, K. Raghavachari, J. S. Binkley, C. Gonzalez, D. J. Defrees, D. J. Fox, R. A. Whitesides, R. Seeger, C. F. Melius, J. Baker, R. L. Martin, L. R. Kahn, J. J. P. Stewart, E. M. Fluder, S. Topiol, and J. A. Pople, Gaussian 88 (Gaussian, Inc., Pittsburgh, PA, 1988).
  10. M. W. Wong, P. M. W. Gill, R. H. Nobes, and L. Radom, J. Phys. Chem. 92, 4875 (1988).
  11. When the d exponents of Wong et al. (Ref. 10) are used rather than HF optimized exponents, the atomization energies of the eight AHn hydrides in Table II are in better agreement with experiment (average absolute deviation of 0.99 kcal/mol) compared to G1 theory (deviation of 1.43 kcal/mol). However, when we considered five two-heavy atom diatomics in Table II (Si2, P2, S2, Cl2, ClO) the D0 values computed using the d exponents of Wong et al. (Ref. 10) were in worse agreement (deviation of 1.56 kcal/mol) compared to G1 theory (deviation of 1.26 kcal/mol).
  12. Computed atomization energies for several one-heavy atom hydrides (HCl, H2S) and diatomics (CS, Cl2, and S2) using the neutral atom basis set of McLean and Chandler are smaller than those obtained using Gl theory. The difference is negligible for the one-heavy atom hydrides (0.1–0.2 kcal/mol) and is up to 1 kcal/mol for the diatomics. Since Gl theory as formulated in this paper tends to give atomization energies that are too low (15 out of 23 species in Table II, Sec. III), the use of the negative ion basis set is preferable.
  13. Carnegie-Mellon Quantum Chemistry Archive, edited by R. A. Whiteside, M. J. Frisch, and J. A. Pople (Carnegie-Mellon University, Pittsburgh, PA).
  14. M. W. Chase, Jr., C. A. Davies, J. R. Downey, Jr., D. J. Frurip, R. A. McDonald, and A. N. Syverud, J. Phys. Chem. Ref. Data 14, Suppl. No. 1 (1985).
  15. K. Huber and G. Herzberg, Molecular Spectra and Molecular Structure 4. Constants of Diatomic Molecules (Van Nostrand, Princeton, 1979).
  16. S. Lias et al. J. Phys. Chem. Ref. Data 17, Suppl. No. 1 (1988).
  17. D. D. Wagman, W. H. Evans, V. B. Parker, R. H. Schumm, I. Halow, S. M. Bailey, K. L. Churney, and R. L. Nutall, J. Phys. Chem. Ref. Data 11, Suppl. No. 2 (1982).
  18. A. G. Gaydon, Dissociation Energies (Chapman and Hall, London, 1968).
  19. L. A. Curtiss and J. A. Pople, J. Phys. Chem. 92, 894 (1988).
  20. J. A. Pople, P. v. R. Schleyer, J. Kaneti, and G. W. Spitznagel, Chem. Phys. Lett. 145, 359 (1988).
  21. K. A. Gingerich, J. Phys. Chem. 73, 2735 (1969).
  22. B. Coquart and J. C. Prudhomme, J. Mol. Spectrosc. 87, 75 (1981).
  23. F. Grein and A. Kapur, J. Mol. Spectrosc. 99, 25 (1983).
  24. K. A. Peterson and R. C. Woods, J. Chem. Phys. 89, 4929 (1988).
  25. M. W. Wong and L. Radom, J. Phys. Chem. 94, 638 (1990).
  26. For BeO, E(MP4/6-311G**) = −89.704 59, Delta(+) = −5.44, Delta(2df) = −48.30, Delta(QCI) = +11.82, Delta(HLC) = −24.56, Delta(ZPE) = +3.54, E0 = −89.767 53. For CF, E(MP4/6-311G**) = −137.525 22, Delta(+) = −6.61, Delta(2df) = −66.58, Delta(QCI) = −0.36, Delta(HLC) = −30.89, Delta(ZPE) = +2.87, E0 = −137.626 79 (units are the same as in Table I).
  27. C. W. Bauschlicher, B. H. Lengsfield, and B. Liu, J. Chem. Phys. 77, 4084 (1982).
  28. S. R. Langhoff, C. W. Bauschlicher, and H. Partridge, J. Chem. Phys. 84, 1687 (1986).
  29. B. J. Garrison and W. A. Goddard, J. Chem. Phys. 87, 1307 (1987).
  30. C. W. Bauschlicher and S. R. Langhoff, J. Chem. Phys. 87, 2919 (1987).
  31. M. Roy and T. B. McMahon, J. Organic Mass Spectrosc. 17, 392 (1982).

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