Theoretical evidence for a bound doubly-excited 1B2(C 1 s, n → π*2) state in H2CO below the C 1 s ionization threshold

Journal of Chemical Physics

Volumn 113, Issue 16, 2000, Pages 6716-6723

  Trofimov, A B ^a   Gromov, E V ^a   Moskovskaya, T E ^a   Schirmer, J ^b  

^a IRKUTSK STATE UNIVERSITY   (Russian Federation)

^b UNIVERSITY OF HEIDELBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

APPROXIMATION THEORY; DISSOCIATION; ELECTRONIC DENSITY OF STATES; ELECTRONIC STRUCTURE; IONIZATION; MOLECULAR STRUCTURE; PHASE EQUILIBRIA; POTENTIAL ENERGY; SPECTROSCOPY; THERMODYNAMIC STABILITY;

ELECTRON EXCITATION SPECTRUM; EXCITED STATE; MULTIREFERENCE CONFIGURATION INTERACTION APPROACH; ZERO POINT VIBRATIONAL ENERGY;

FORMALDEHYDE;

EID: 0034297863     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.1311296     Document Type: Article

References (25)

1. J. Schirmer, A. Barth, and F. Tarantelli, Chem. Phys. 122, 9 (1988).
2. A. W. K. Leung, J. G. McCaffrey, and W. H. Breckenridge, J. Chem. Phys. 109, 7777 (1998); P. J. Bruna and J. S. Wright, Can. J. Chem. 74, 998 (1996); Y. Liu, J. Li, M. Xue, D. Chen, L. Li, and G.-H. Jeung, J. Chem. Phys. 103, 7213 (1995).
3. A. W. K. Leung, J. G. McCaffrey, and W. H. Breckenridge, J. Chem. Phys. 109, 7777 (1998); P. J. Bruna and J. S. Wright, Can. J. Chem. 74, 998 (1996); Y. Liu, J. Li, M. Xue, D. Chen, L. Li, and G.-H. Jeung, J. Chem. Phys. 103, 7213 (1995).
4. A. W. K. Leung, J. G. McCaffrey, and W. H. Breckenridge, J. Chem. Phys. 109, 7777 (1998); P. J. Bruna and J. S. Wright, Can. J. Chem. 74, 998 (1996); Y. Liu, J. Li, M. Xue, D. Chen, L. Li, and G.-H. Jeung, J. Chem. Phys. 103, 7213 (1995).
5. M. Neeb, A. Kivimäki, B. Kempgens, H. M. Köppe, J. Feldhaus, and A. M. Bradshaw, Phys. Rev. Lett. 76, 2250 (1996); H. M. Köppe, B. Kempgens, A. L. D. Kilcoyne, J. Feldhaus, and A. M. Bradshaw, Chem. Phys. Lett. 260, 223 (1996).
6. M. Neeb, A. Kivimäki, B. Kempgens, H. M. Köppe, J. Feldhaus, and A. M. Bradshaw, Phys. Rev. Lett. 76, 2250 (1996); H. M. Köppe, B. Kempgens, A. L. D. Kilcoyne, J. Feldhaus, and A. M. Bradshaw, Chem. Phys. Lett. 260, 223 (1996).
7. G. Remmers, M. Domke, A. Puschmann, T. Mandel, C. Xue, G. Kaindl, E. Hudson, and D. A. Shirley, Phys. Rev. A 46, 3935 (1992).
8. A. P. Hitchcock and C. E. Brion, J. Electron Spectrosc. Relat. Phenom. 19, 231 (1980).
9. G. F. Adams, G. D. Bent, R. J. Bartlett, and G. D. Purvis, J. Chem. Phys. 75, 834 (1981); H. Nakano, K. Nakayama, K. Hirao, and M. Dupuis, ibid. 106, 4912 (1997); Y. Yamaguchi, S. S. Wesolowski, T. J. Van Huis, and H. F. Schaefer III, ibid. 108, 5281 (1998).
10. G. F. Adams, G. D. Bent, R. J. Bartlett, and G. D. Purvis, J. Chem. Phys. 75, 834 (1981); H. Nakano, K. Nakayama, K. Hirao, and M. Dupuis, ibid. 106, 4912 (1997); Y. Yamaguchi, S. S. Wesolowski, T. J. Van Huis, and H. F. Schaefer III, ibid. 108, 5281 (1998).
11. G. F. Adams, G. D. Bent, R. J. Bartlett, and G. D. Purvis, J. Chem. Phys. 75, 834 (1981); H. Nakano, K. Nakayama, K. Hirao, and M. Dupuis, ibid. 106, 4912 (1997); Y. Yamaguchi, S. S. Wesolowski, T. J. Van Huis, and H. F. Schaefer III, ibid. 108, 5281 (1998).
12. The ROHF approach is of course only approximately valid for studies of the core-hole states as they are not the lowest states of a given symmetry. However, the great energy gap and the sharp distinction in electron density distribution between the core- and the lower-lying valence-excited states prevent the self-consistent field (SCF) procedure from a variational collapse.
13. S. Huzinaga, J. Chem. Phys. 42, 1293 (1965).
14. J. Schirmer, A. B. Trofimov, K. J. Randall, J. Feldhaus, A. M. Bradshaw, Y. Ma, C. T. Chen, and F. Sette, Phys. Rev. A 47, 1136 (1993).
15. T. H. Dunning Jr., J. Chem. Phys. 90, 1007 (1989).
16. 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, Jr., J. Comput. Chem. 14, 1347 (1993).
17. V. R. Saunders and J. H. van Lenthe, Mol. Phys. 48, 923 (1983).
18. Program written by M. F. Guest, J. H. van Lenthe, J. Kendrick et al., with contributions from R. D. Amos, R. J. Buenker, M. Dupuis et al. The package is derived from the original GAMESS code due to M. Dupuis, D. Spangler, and J. Wendoloski, NRCC Software Catalog, Vol. 1, Program No. QG01 (GAMESS), 1980.
19. R. J. Gillespie, Molecular Geometry (Van Nostrand Reinhold, London, 1972).
20. S. Tsunekawa, J. Soc. Phys. Jpn. 33, 167 (1972).
21. P. R. Buenker, Annu. Rev. Phys. Chem. 34, 59 (1983).
22. D. J. Clouthier and D. A. Ramsay, Annu. Rev. Phys. Chem. 34, 31 (1983).
23. The coupled perturbed Hartree-Fock (CPHF) equations required for Hessian evaluation could not been solved at the located stationary point, probably due to the increased inherent instability of the ROHF orbitals describing core-hole Rydberg state. Although we failed to compute vibrational frequencies which could prove directly that the true minimum was found, no other stationary point could be obtained even when less-symmetric guesses were used in the geometry optimization procedure.
24. E. R. Davidson and L. E. McMurchie, in Excited States, edited by E. C. Lim (Academic, New York, 1982), Vol. 5, pp. 1-39.
25. P. J. Bruna and S. D. Peyerimhoff, in Ab Initio Methods in Quantum Chemistry, edited by K. P. Lawley (Wiley, New York, 1987), Vol. 1, pp. 1-97.