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Dissection of rovibronic band structure by polarization-resolved degenerate four-wave mixing spectroscopy

J. Chem. Phys. 119, 887 (2003); doi:10.1063/1.1579472

Issue Date: 8 July 2003

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Alfredo E. Bracamonte and Patrick H. Vaccaro
Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107
Judicious selection of polarization characteristics in degenerate four-wave mixing (DFWM) spectroscopy is shown to provide a facile and robust means for discriminating rovibronic features according to their changes in rotational angular momentum, DeltaJ. Building upon a perturbative (weak-field) treatment of the resonant DFWM response, theoretical analyses are presented for a collinear arrangement of linearly polarized electromagnetic waves that interact with an isotropic ensemble of gas-phase target molecules. The polarization unit vectors for two input fields (E1 and E3) are presumed to be fixed along the Y-axis (phi1 = phi3 = pi/2), while the remaining incident field (E2) has its orientation within the transverse X–Y plane specified by angular coordinate phi2. For phi2 = pi/4, complete elimination of high-J Q-branch (DeltaJ = 0) and P-/R-branch (DeltaJ = ±1) structure is found to occur when the detected direction of linear polarization is switched between the limiting values of phi4,Q = –18.43° and phi4,P/R = +26.57°, respectively. These predictions are corroborated experimentally by probing the tunneling-split origin region of the tropolone à 1B2–X-tilde 1A1 (pi*<--pi) absorption system under ambient, bulk-gas conditions. Other polarization-based schemes for rovibronic branch suppression are discussed as are the effects incurred by (strong-field) optical saturation phenomena. The implementations of DFWM suggested by this work should prove useful for dissecting and unraveling the congested spectra often exhibited by massive polyatomic species. ©2003 American Institute of Physics.
History: Received 14 February 2003; accepted 14 April 2003
Permalink: http://link.aip.org/link/?JCPSA6/119/887/1
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KEYWORDS and PACS

Keywords
PACS
  • 33.20.Wr
    Vibronic, rovibronic, and rotation-electron-spin interactions (molecular spectra)
  • 42.65.Hw
    Optical phase conjugation; photorefractive and Kerr effects
  • 33.20.Vq
    Vibration-rotation analysis (molecular spectra)
  • 42.50.Gy
    Effects of atomic coherence on propagation, absorption, and amplification of light; electromagnetically induced transparency and absorption
  • YEAR: 2003

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (52)
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For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. S. Mukamel, Principles of Nonlinear Optical Spectroscopy (Oxford University Press, New York, 1995).
  2. W. Demtröder, Laser Spectroscopy: Basic Concepts and Instrumentation, 2nd ed. (Springer-Verlag, Berlin, 1996).
  3. Nonlinear Spectroscopy for Molecular Structure Determination, edited by R. W. Field, E. Hirota, J. P. Maier, and S. Tsuchiya (Blackwell Scientific, London, 1998).
  4. R. L. Farrow and D. J. Rakestraw, Science 257, 1894 (1992).
  5. P. H. Vaccaro, in Molecular Dynamics and Spectroscopy by Stimulated Emission Pumping, edited by H.-L. Dai and R. W. Field (World Scientific, Singapore, 1995), Vol. 4, p. 1.
  6. P. H. Vaccaro, in Nonlinear Spectroscopy for Molecular Structure Determination, edited by E. Hirota, R. W. Field, J. P. Maier, and S. Tsuchiya (Blackwell Scientific, London, 1998), p. 75.
  7. D. C. Hanna, M. A. Yuratich, and D. Cotter, Nonlinear Optics of Free Atoms and Molecules (Springer-Verlag, Berlin, 1979); J. F. Reintjes, Nonlinear Optical Parametric Processes in Liquids and Gases (Academic, New York, 1984).
  8. S. A. J. Druet and J. P. Taran, Prog. Quantum Electron. 7, 1 (1981);
  9. B. Attal-Trétout, P. Monot, and K. Müller-Dethlefs, Mol. Phys. 73, 1257 (1991);
  10. I. Aben, W. Ubachs, G. van der Zwan, and W. Hogervorst, ibid. 76, 591 (1992);
  11. Chem. Phys. 169, 113 (1993);
  12. A. Zilian and J. C. Wright, Mol. Phys. 87, 1261 (1996).
  13. H. Bervas, S. Le Boiteux, L. Labrunie, and B. Attal-Trétout, Mol. Phys. 79, 911 (1993);
  14. L. A. Rahn and M. S. Brown, Opt. Lett. 19, 1249 (1994);
  15. S. Williams, E. A. Rohlfing, L. A. Rahn, and R. N. Zare, J. Chem. Phys. 106, 3090 (1996).
  16. S. Williams, R. N. Zare, and L. A. Rahn, J. Chem. Phys. 101, 1072 (1994).
  17. R. G. Bray and R. M. Hochstrasser, Mol. Phys. 31, 1199 (1976).
  18. W. M. McClain, J. Chem. Phys. 58, 324 (1973).
  19. W. M. McClain, Acc. Chem. Res. 7, 129 (1974);
    20. W. M. McClain and R. A. Harris, Excited States 3, 1 (1977);
    D. M. Friedrich and W. M. McClain, Annu. Rev. Phys. Chem. 31, 559 (1980).
  20. J. B. Halpern, H. Zacharias, and R. Wallenstein, J. Mol. Spectrosc. 79, 1 (1980).
  21. S. E. Bialkowski and W. A. Guillory, Chem. Phys. 55, 229 (1981);
    22. R. N. Dixon, J. M. Bayley, and M. N. R. Ashfold, ibid. 84, 21 (1984).
  22. M. N. R. Ashfold and J. D. Howe, Annu. Rev. Phys. Chem. 45, 57 (1994);
    23. M. N. R. Ashfold, in Nonlinear Spectroscopy for Molecular Structure Determination, edited by E. Hirota, R. W. Field, J. P. Maier, and S. Tsuchiya (Blackwell Scientific, London, 1998), p. 127;
    D. Ascenzi, S. R. Langford, M. N. R. Ashfold, and A. J. Orr-Ewing, Phys. Chem. Chem. Phys. 3, 29 (2001).
  23. H. Katô, R. Clark, and A. J. McCaffery, Mol. Phys. 31, 943 (1976);
    24. A. J. Bain and A. J. McCaffery, J. Chem. Phys. 80, 5883 (1984);
    83, 2627 (1985).
  24. R. N. Zare, Angular Momentum: Understanding Spatial Aspects in Chemistry and Physics (Wiley, New York, 1988).
  25. M. Raab, G. Höning, R. Castell, and W. Demtröder, Chem. Phys. Lett. 66, 307 (1979);
    26. V. Stert and R. Fisher, Appl. Phys. 17, 151 (1978);
    M. Raab, G. Höning, W. Demtröder, and C. R. Vidal, J. Chem. Phys. 76, 4370 (1982);
    M. H. Kabir, S. Kasahara, W. Demtröder et al., Chem. Phys. 283, 237 (2002).
  26. F. Metz, W. E. Howard, L. Wunsch, H. J. Neusser, and E. W. Schlag, Proc. R. Soc. London, Ser. A 363, 381 (1978).
  27. D. M. Friedrich and W. M. McClain, Chem. Phys. Lett. 32, 541 (1975);
    28. J. R. Lombardi, D. M. Friedrich, and W. M. McClain, ibid. 38, 213 (1976);
    L. Wunsch, H. J. Neusser, and E. W. Schlag, ibid. 38, 216 (1976);
    L. Wunsch, F. Metz, H. J. Neusser, and E. W. Schlag, J. Chem. Phys. 66, 386 (1977);
    R. L. Whetten, S. G. Grubb, C. E. Otis, A. C. Albrecht, and E. R. Grant, ibid. 82, 1115 (1984).
  28. R. Teets, R. Feinberg, T. W. Hänsch, and A. L. Schawlow, Phys. Rev. Lett. 37, 683 (1976);
    29. C. Wieman and T. W. Hänsch, ibid. 26, 1170 (1976).
  29. R. E. Teets, F. V. Kowalski, W. T. Hill, N. Carison, and T. W. Hänsch, Proc. SPIE 113, 80 (1977).
  30. P. H. Vaccaro, Ph.D., Massachusetts Institute of Technology, 1986.
  31. T. A. Reichardt, F. DiTeodoro, R. L. Farrow, S. Roy, and R. P. Lucht, J. Chem. Phys. 113, 2263 (2000).
  32. T. A. W. Wasserman, P. H. Vaccaro, and B. R. Johnson, J. Chem. Phys. 106, 6314 (1997);
    33. 108, 7713 (1997).
  33. A. C. P. Alves and J. M. Hollas, Mol. Phys. 23, 927 (1972);
    34. 25, 1305 (1973).
  34. A. C. P. Alves, J. M. Hollas, H. Musa, and T. Ridley, J. Mol. Spectrosc. 109, 99 (1985).
  35. T. A. W. Wasserman, P. H. Vaccaro, and B. R. Johnson, J. Chem. Phys. 116, 10099 (2002).
  36. P. N. Butcher and D. Cotter, The Elements of Nonlinear Optics (Cambridge University Press, Cambridge, England, 1990).
  37. R. L. Abrams, J. F. Lam, R. C. Lind, D. G. Steel, and P. F. Liao, in Optical Phase Conjugation, edited by R. A. Fisher (Academic, San Diego, 1983), p. 211.
  38. The weak-field calculation of (unsaturated) four-wave mixing response is performed most expeditiously through use of time-dependent perturbation theory, with successive matter–field interactions leading to progressively higher-order terms in a perturbative expansion that culminates ultimately in the evaluation of P(3)(t). For frequency-domain implementations of DFWM spectroscopy, the quantity epsilon <sub>4</sub><sup>*</sup>·P(3)(omegas), which represents the Fourier transformation of epsilon <sub>4</sub><sup>*</sup>·P(3)(t), usually appears in derived signal expressions.
  39. A. J. Orr-Ewing and R. N. Zare, Annu. Rev. Phys. Chem. 45, 315 (1994).
  40. T. Müller, T. A. W. Wasserman, P. H. Vaccaro, and B. R. Johnson, J. Chem. Phys. 108, 4 (1998).
  41. K. Blum, Density Matrix Theory and Applications (Plenum, New York, 1996).
  42. S. Gerstenkorn, J. Verges, and J. Chevillard, Atlas du Spectre d'Absorption de la Molécule d'Iode (10000–14000 cm–1) (Editions du C.N.R.S., Paris, 1982).
  43. A. E. Bracamonte and P. H. Vaccaro (unpublished).
  44. R. P. Lucht, R. L. Farrow, and D. J. Rakestraw, J. Opt. Soc. Am. B 10, 1508 (1993);
    45. T. A. Reichardt and R. P. Lucht, ibid. 13, 1107 (1996);
    13, 2807 (1996);
    T. A. Reichardt, R. P. Lucht, and P. M. Danehy, ibid. 15, 2566 (1998);
    T. A. Reichardt and R. P. Lucht, J. Chem. Phys. 111, 10008 (1999).
  45. M. Nakano, K. Yamaguchi, Y. Matsuzaki, K. Tanaka, and T. Yamabe, J. Chem. Phys. 102, 2986 (1995);
    46. M. Nakano and K. Yamaguchi, Chem. Phys. Lett. 234, 323 (1995).
  46. D. A. Coppeta, P. L. Kelly, P. J. Harshman, and T. K. Gustafson, Phys. Rev. A 53, 925 (1996).
  47. V. Krüger, M. Dumont, S. LeBoiteux, Y. J. Picard, F. Chaussard, and B. Attal-Trétout, Phys. Rev. A 64, 012716 (2001);
    48. 64, 012717 (2001).
  48. R. L. Abrams and R. C. Lind, Opt. Lett. 2, 94 (1978);
    49. 3, 205 (1978).
  49. R. L. Vander Wal, R. L. Farrow, and D. J. Rakestraw, in Proceedings of the Twenty-Fourth (International) Symposium on Combustion (Combustion Institute, Pittsburgh, PA, 1992), p. 1653;
    50. M. S. Brown, L. A. Rahn, and T. Dreier, Opt. Lett. 17, 76 (1992);
    G. J. Germann and D. J. Rakestraw, Science 264, 1750 (1994);
    G. J. Germann, R. L. Farrow, and D. J. Rakestraw, J. Opt. Soc. Am. B 12, 25 (1995).
  50. R. L. Farrow, T. Dreier, and D. J. Rakestraw, J. Opt. Soc. Am. B 9, 1770 (1992).
  51. S. Williams, R. N. Zare, and L. A. Rahn, J. Chem. Phys. 101, 1093 (1994).
  52. Quantities, Units, and Symbols in Physical Chemistry, edited by I. Mills, T. Cvitas, K. Homann, N. Kallay, and K. Kuchitsu (Blackwell Scientific, London, 1993).
  53. R. L. Redington and R. W. Field, Spectrochim. Acta, Part A 45, 41 (1989);
    54. R. L. Redington, Y. Chen, G. J. Scherer, and R. W. Field, J. Chem. Phys. 88, 627 (1988).
  54. R. C. Hilborn, Am. J. Phys. 50, 982 (1982).
  55. Y. Tomioka, M. Ito, and N. Mikami, J. Phys. Chem. 87, 4401 (1983);
    56. H. Sekiya, Y. Nagashima, and Y. Nishimura, J. Chem. Phys. 92, 5761 (1990).
  56. R. L. Redington, T. E. Redington, and J. M. Montgomery, J. Chem. Phys. 113, 2304 (2000).
  57. R. L. Redington, J. Chem. Phys. 92, 6447 (1990);
    58. 113, 2319 (2000).
  58. K. Tanaka, H. Honjo, T. Tanaka, H. Kohguchi, Y. Ohshima, and Y. Endo, J. Chem. Phys. 110, 1969 (1999).

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