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Direct vibrational self-consistent field method: Applications to H2O and H2CO

J. Chem. Phys. 113, 1005 (2000); doi:10.1063/1.481881

Issue Date: 15 July 2000

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Kiyoshi Yagi
Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan

Tetsuya Taketsugu
Department of Chemistry, Faculty of Science, Ochanomizu University, Tokyo 112-8610, Japan

Kimihiko Hirao
Department of Applied Chemistry, Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan

Mark S. Gordon
Department of Chemistry, Iowa State University, Ames, Iowa 50011
The vibrational self-consistent field (VSCF) and virtual configuration interaction (VCI) methods are directly combined with ab initio electronic structure calculations for evaluations of the potential energy at VSCF quadrature points. Referred to as direct VSCF and direct VCI, respectively, these methods have been applied to evaluations of anharmonic vibrational energy levels of H2O and H2CO at the second-order Møller–Plesset MP2/aug-cc-pVTZ and MP2/cc-pVTZ computational levels, respectively. The purpose of the present study is to develop a direct methodology for vibrational state calculations by examining the accuracy of the results, as well as their computational costs. In addition, the accuracy and applicability of two approximate potential energy surfaces (PES), a quartic force field (QFF), and the PES determined by the modified-Shepard interpolation method (Int-PES), are investigated via comparisons of calculated energy levels of vibrational states with those derived by the direct methods. The results are analyzed in terms of three considerations: (i) truncations of higher-order intercoordinate couplings in the PES; (ii) mode–mode coupling effects; (iii) approximations in ab initio electronic structure methods. In the direct VCI calculations, the average absolute deviations in fundamental frequencies relative to the experimental values are 9.3 cm–1(H2O) and 34.7 cm–1(H2CO). The corresponding values evaluated with approximate PESs relative to those derived by the direct method are 35.0 cm–1 (QFF) and 15.3 cm–1 (Int-PES) for H2O, and 6.3 cm–1 (QFF) and 10.3 cm–1 (Int-PES) for H2CO. ©2000 American Institute of Physics.
History: Received 14 March 2000; accepted 20 April 2000
Permalink: http://link.aip.org/link/?JCPSA6/113/1005/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.15.Ne
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Self-consistent-field methods
  • 31.25.Qm
    Electronic structure of atoms, molecules and their ions: theory Electron correlation calculations for atoms and molecules Electron correlation calculations for polyatomic molecules
  • 31.90.+s
    Electronic structure of atoms, molecules and their ions: theory Other topics in the theory of the electronic structure of atoms, molecules, and their ions (restricted to new topics in section 31)
  • 33.15.Mt
    Molecular properties and interactions with photons Properties of molecules and molecular ions Rotation, vibration, and vibration–rotation constants
  • YEAR: 2000

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0021-9606 (print)   1089-7690 (online)
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REFERENCES (51)
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  1. M. S. Gordon, G. M. Chaban, and T. Taketsugu, J. Phys. Chem. 100, 11512 (1996).
  2. J. J. P. Stewart, L. P. Davis, and L. W. Burggraf, J. Comput. Chem. 8, 1117 (1987).
  3. S. A. Maluendes and M. Dupuis, J. Chem. Phys. 93, 5902 (1990).
  4. T. Helgaker, E. Uggerund, and H. J. A. Jensen, Chem. Phys. Lett. 173, 145 (1990);
    5. E. Uggerund and T. Helgaker, J. Am. Chem. Soc. 114, 4265 (1992).
  5. W. Chen, W. L. Hase, and H. B. Schlegel, Chem. Phys. Lett. 228, 436 (1994).
  6. T. Taketsugu and M. S. Gordon, J. Phys. Chem. 99, 8462 (1995);
    7. 99, 14597 (1995).
  7. T. Taketsugu and M. S. Gordon, J. Chem. Phys. 103, 10042 (1995).
  8. T. Taketsugu and T. Hirano, J. Chem. Phys. 104, 6081 (1996).
  9. T. Taketsugu, T. Yanai, K. Hirao, and M. S. Gordon, J. Mol. Struct.: THEOCHEM 451, 163 (1998).
  10. T. Takata, T. Taketsugu, K. Hirao, and M. S. Gordon, J. Chem. Phys. 109, 4281 (1998).
  11. Y. Kumeda, Y. Minarmi, K. Takano, T. Taketsugu, and T. Hirano, J. Mol. Struct.: THEOCHEM 458, 285 (1999).
  12. G. M. Chaban, J. O. Jung, and R. B. Gerber, J. Chem. Phys. 111, 1823 (1999).
  13. J. M. Bowman, J. Chem. Phys. 68, 608 (1978).
  14. R. B. Gerber and M. A. Ratner, Chem. Phys. Lett. 68, 195 (1979).
  15. J. M. Bowman, Acc. Chem. Res. 19, 202 (1986).
  16. R. B. Gerber and M. A. Ratner, Adv. Chem. Phys. 70, 97 (1998).
  17. J. O. Jung and R. B. Gerber, J. Chem. Phys. 105, 10332 (1996).
  18. L. S. Norris, M. A. Ratner, A. E. Roitberg, and R. B. Gerber, J. Chem. Phys. 106, 11261 (1996).
  19. K. M. Christoffel and J. M. Bowman, Chem. Phys. Lett. 85, 220 (1982).
  20. F. L. Tobin and J. M. Bowman, Chem. Phys. 47, 151 (1980).
  21. MULTIMODE, a variational code for the calculation of rovibrational energies of large polyatomic molecules, S. Carter and J. M. Bowman, with contributions from N. Handy;
    22. S. Carter, S. J. Culik, and J. M. Bowman, J. Chem. Phys. 107, 10458 (1997);
    S. Carter and J. M. Bowman, 108, 4397 (1998);
    S. Carter, J. M. Bowman, and N. Handy, Theor. Chem. Acc. 100, 191 (1998);
    for on-line documentation, etc. visit www.emory.edu/CHEMISTRY/faculty/bowman/multimode
  22. F. Dzegilenko, J. M. Bowman, and S. Carter, J. Chem. Phys. 109, 7506 (1998).
  23. S. Carter, H. M. Shnider, and J. M. Bowman, J. Chem. Phys. 110, 8417 (1999).
  24. J. M. Bowman and H. Shnider, J. Chem. Phys. 110, 4428 (1999).
  25. K. M. Christoffel and J. M. Bowman, J. Phys. Chem. A 103, 3020 (1999).
  26. S. Carter and J. M. Bowman, J. Phys. Chem. A 104, 2355 (2000).
  27. C. Møller and M. S. Plesset, Phys. Rev. 46, 618 (1934).
  28. J. Ischtwan and M. A. Collins, J. Chem. Phys. 100, 8080 (1994).
  29. M. A. Collins, in New Method in Computational Quantum Mechanics, edited by I. Prigogine and S. A. Rice (Wiley, New York, 1996), p. 389.
  30. K. C. Thompson, M. J. T. Jordan, and M. A. Collins, J. Chem. Phys. 108, 564 (1998);
    31. 108, 8302 (1998).
  31. T. Ishida and G. C. Schatz, J. Chem. Phys. 107, 3558 (1997);
    32. Chem. Phys. Lett. 298, 285 (1998).
  32. T. Taketsugu, N. Watanabe, and K. Hirao, J. Chem. Phys. 111, 3410 (1999).
  33. J. K. G. Watson, Mol. Phys. 15, 479 (1968).
  34. G. D. Fletcher, M. W. Schmidt, and M. S. Gordon, Adv. Chem. Phys. 110, 267 (1999).
  35. M. W. Schmidt, G. D. Fletcher, B. M. Bode, and M. S. Gordon, Comp. Phys. Commun. (in press).
  36. R. A. Kendall, T. H. Dunning, Jr., and R. J. Harrison, J. Chem. Phys. 96, 6796 (1992).
  37. T. H. Dunning, Jr., J. Chem. Phys. 90, 1007 (1989).
  38. M. W. Schmidt, K. K. Baldridge, J. A. Boatz, S. T. Elbert, M. S. Gordon, J. H. Jensen, S. Koseki, N. Matsunaga, K. A. Nguyen, S. Su, T. L. Windus, M. Dupuis, and J. A. Montgomery, J. Comput. Chem. 14, 1347 (1993).
  39. W. J. Hehre, R. Ditchfield, and J. A. Pople, J. Chem. Phys. 56, 2257 (1972).
  40. D. O. Harris, G. G. Engerholm, and W. D. Gwinn, J. Chem. Phys. 43, 1515 (1965).
  41. J. Echave and D. C. Clary, Chem. Phys. Lett. 190, 225 (1992).
  42. G. Herzberg, Electronic Spectra of Polyatomic Molecules (Van Nostrand, Princeton, 1966).
  43. D. F. Smith and J. Overend, Spectrochim. Acta A 28, 471 (1972).
  44. H. Romanowski, J. M. Bowman, and L. B. Harding, J. Chem. Phys. 82, 4155 (1985).
  45. J. M. L. Martin, T. J. Lee, and P. R. Taylor, J. Mol. Spectrosc. 160, 105 (1993).
  46. M. Allegrini, J. W. C. Johns, and A. R. W. McKellar, J. Mol. Spectrosc. 67, 476 (1977).
  47. L. R. Brown, R. H. Hunt, and A. S. Pine, J. Mol. Spectrosc. 75, 406 (1979).
  48. C. Brechignac, J. W. C. Johns, A. R. W. McKellar, and M. Wong, J. Mol. Spectrosc. 96, 353 (1982).
  49. H. H. Blau, Jr. and H. H. Nielsen, J. Mol. Spectrosc. 1, 124 (1957).
  50. T. Nakagawa, K. Yamada, and K. Kuchitsu, J. Mol. Spectrosc. 63, 485 (1976).
  51. D. J. Clouthier and D. A. Ramsay, Annu. Rev. Phys. Chem. 34, 31 (1983).

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