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Two-photon dissociation of vibrationally excited HD+: The inhomogeneous differential equation approach

J. Chem. Phys. 85, 1403 (1986); doi:10.1063/1.451229

Issue Date: 1 August 1986

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Cecil Laughlin, Krishna K. Datta, and Shih-I Chu
Department of Chemistry, University of Kansas, Lawrence, Kansas 66045
We extend the inhomogenous-differential-equation (IDE) approach of Dalgarno and Lewis for a detailed study of two-photon dissociation (TPD) of HD+ from high vibrational levels of the 1ssigmag electronic state. Contrary to the H<sup> + </sup><sub>2</sub> case, where the TPD cross sections sigma<sup>(2)</sup><sub>L</sub> are largest near TPD thresholds and decrease monotonically with increasing photon energy, the HD+ cross sections are characterized by rich resonant and interference structures. We present sigma<sup>(2)</sup><sub>L</sub> results for TPD from the initial vi =6, 8, 10, 12, 14, 16, and ji=0 levels as well as from vi=14, ji=0, 2, 4 levels for a wide range of wavelengths of linearly polarized radiation accessible by CO2 and CO lasers. It is found that while there are four TPD pathways, the channel 1ssigmag(vi ji)-->omega 1ssigmag(v, j=ji±1) -->omega2psigmau(k, j f=j±1) dominates the two-photon process in most of the cases we have studied. Further, the results show that sigma<sup>(2)</sup><sub>L</sub> increases rather rapidly as the initial vibrational quantum number vi increases, indicating that the hereronuclear diatomic molecules in high vibrational levels can be efficiently two-photon dissociated by IR lasers. Consequently molecular structures near the dissociation limit may be conveniently probed by two-photon spectroscopy—as has indeed been demonstrated recently by experiments. Our sigma<sup>(2)</sup><sub>L</sub> results thus provide complementary information to the HD+ spectroscopic data obtained recently by Carrington et al. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 3 February 1986; accepted 23 April 1986
Permalink: http://link.aip.org/link/?JCPSA6/85/1403/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.80.Gj
    Molecular spectra and interactions of molecules with photons Photon interactions with molecules Diffuse spectra; predissociation, photodissociation
  • 33.80.Wz
    Molecular spectra and interactions of molecules with photons Photon interactions with molecules Other multiphoton processes
  • YEAR: 1986

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
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REFERENCES (23)
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  10. J. M. Schulman, R. Detrano, and J. I. Musher, Phys. Rev. A 5, 1125 (1972).
  11. C. Laughlin, S.-I. Chu, and K. K. Datta, in Abstracts of Contributed Papers, 13th ICPEAC, edited by J. Eichler, W. Fritsch, I. V. Hertel, N. Stolterfoht, and U. Wille (North-Holland, Amsterdam, 1983), p. 75.
  12. M. K. Chakrabarti, S. S. Bhattacharya, K. K. Datta, and S. Saha, Chem. Phys. Lett. 113, 492 (1985);
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    (c) C. Leforestier and R. E. Wyatt, Phys. Rev. A 25, 1250 (1982).
  14. For a recent review on nonperturbative approaches to intense field multiphoton excitation, ionization, and dissociation processes, see S.-I. Chu, Adv. At. Mol. Phys. 21, 197 (1985).
  15. See, for example, O. Atabek, M. Jacon, and R. Lefebvre, J. Chem. Phys. 72, 2670, 2683 (1980);
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  16. P. Lambropoulos, Adv. At. Mol. Phys. 12, 87 (1976).
  17. A. R. Edmonds, Angular Momentum in Quantum Mechanics (Princeton University, Princeton, 1957).
  18. C.-E. Froberg, Introduction to Numerical Analysis (Addison-Wesley, Reading, MA, 1965).
  19. (a) D. R. Bates, K. Ledsham, and A. L. Stewart, Philos. Trans. R. Soc. London Ser. A 246, 212 (1953);
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  20. T.-S. Ho, S.-I. Chu, and C. Laughlin, J. Chem. Phys. 81, 788 (1984).
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  24. Contrary to the neutral molecule HD whose permanent dipole moment is vanishingly small, the heteronuclear molecular ion HD+ has a substantial dipole moment even within the Born-Oppenheimer approximation. This is because the center of mass and center of charge in HD+ are separated. The effect of nonadiabatic interactions on the dipole moment of HD+ is very slight (of the order of 110−3 times smaller). For details, see Ref. 21.
  25. Comparisons were made with available experimental data in Refs. 3(a) and 3(b) and with theoretical data in L. Wolniewicz and J. D. Poll, J. Chem. Phys. 73, 6225 (1980).

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