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Solidlike coherent vibronic dynamics in a room temperature liquid: Resonant Raman and absorption spectroscopy of liquid bromine

Source: J. Chem. Phys. 132, 044503 (2010); doi:10.1063/1.3291610

Published 22 January 2010

KEYWORDS and PACS
Keywords
PACS
  • 63.20.Ry
    Anharmonic lattice modes
  • 71.70.Jp
    Nuclear states and interactions (condensed matter)
  • 71.70.Ch
    Crystal and ligand fields
  • 78.30.C-
    Liquids
  • 78.40.Dw
    Visible and ultraviolet spectra of liquids
  • YEAR: 2010
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PUBLICATION DATA
ISSN:
1553-9601 (online)
Publisher:
AIP is a member of CrossRef AIP
Edward T. Branigan, Marie N. van Staveren, and V. Ara Apkarian
Department of Chemistry, University of California, Irvine, California 92697-2025, USA
UV-visible absorption and resonance Raman (RR) spectra of liquid bromine are presented and rigorously interpreted. The RR spectra, which show an anharmonic vibrational progression of up to 30 overtones, define the ground state potential in the range 2.05  Å<r<3.06  Å. The attractive branch of the X-state potential is softened and apparent dissociation limit of the molecule dramatically reduced by ~30% in the liquid phase, indicating an attractive cage-molecule interaction. The excited state potentials (A[prime], B, and C) are extracted from the absorption spectrum. The spectrum is first inverted under assumption of the classical reflection approximation, then corrected by forward simulations through quantum time correlations. The extrapolated B and C potentials are used to simulate RR spectra. Their validity is cross-checked by the interference pattern of the polarized spectra due to two-channel RR scattering. The discrepancy between calculated and observed intensities can be entirely assigned to vibrational dephasing, which is observed to follow the exponential energy gap law—dephasing rates perfectly trace the Birge–Sponer plot of the vibrational progression—suggesting that vibrational dissipation controls the decay of coherence. Despite strong intermolecular electronic interactions and vibrational energy gaps of ~kT, vibrational coherences are long lived: Coherence times range from >=25 to >=2.4  ps between v=1 and v=25. Remarkably, the RR line shapes are skewed toward the red, indicating upchirp in frequencies that develop over a period of 400 fs. Evidently, the molecular vibrations adiabatically follow the solvent cage, which is impulsively driven into expansion during the ~20  fs evolution on the electronically excited state. Liquid bromine retains coherence in ordered sluggish local cages with quadrupolar interactions—dynamics akin to molecules isolated in structured cryogenic rare gas solids. ©2010 American Institute of Physics
History: Received 28 October 2009; accepted 19 December 2009; published 22 January 2010
Permalink: http://link.aip.org/link/?JCPSA6/132/044503/1

REFERENCES (55)

For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. I. U. Goldschleger, G. Kerenskaya, K. C. Janda, and V. A. Apkarian, J. Phys. Chem. A 112, 787 (2008).
  2. P. Buchanan, A. K. Soper, H. Thompson, R. E. Westacott, J. L. Creek, G. Hobson, and C. A. Koh, J. Chem. Phys. 123 (2005).
  3. G. Caglioti and F. P. Ricci, Nuovo Cimento 24, 103 (1962).
  4. C. E. Weir, G. J. Piermari, and S. Block, J. Chem. Phys. 50, 2089 (1969).
  5. K. Mukose, R. Fukano, H. Miyagi, and K. Yamaguchi, J. Phys.: Condens. Matter 14, 10441 (2002).
  6. P. S. Johannsen and W. B. Holzapfel, J. Phys. C 16, 1961 (1983).
  7. T. Kiviniemi, J. Aumanen, P. Myllyperkio, V. A. Apkarian, and M. Pettersson, J. Chem. Phys. 123, 064509 (2005).
  8. H. Stammreich and R. Forneris, J. Chem. Phys. 22, 1624 (1954).
  9. A. J. Melveger, J. W. Brasch, and E. R. Lippinco, Appl. Opt. 9, 11 (1970).
  10. B. S. Ault, W. F. Howard, and L. Andrews, J. Mol. Spectrosc. 55, 217 (1975).
  11. J. Langen, K. P. Lodemann, and U. Schurath, Chem. Phys. 112, 393 (1987).
  12. W. M. Sears, J. L. Hunt, and J. R. Stevens, J. Chem. Phys. 75, 1589 (1981).
  13. F. Cansell, D. Fabre, and J. P. Petitet, Physica B 182, 195 (1992).
  14. R. F. Barrow, T. C. Clark, J. A. Coxon, and K. K. Yee, J. Mol. Spectrosc. 51, 428 (1974).
  15. J. Almy, K. Kizer, R. Zadoyan, and V. A. Apkarian, J. Phys. Chem. A 104, 3508 (2000).
  16. K. P. Huber and G. Herzberg, in NIST Chemistry WebBook, NIST Standard Reference Database Number 69, edited by P. J. Linstrom and W. G. Mallard (National Institute of Standards and Technology, Gaithersburg, MD, 2001).
  17. C. Focsa, H. Li, and P. F. Bernath, J. Mol. Spectrosc. 200, 104 (2000).
  18. C. H. Townes and A. L. Schawlow, Microwave Spectroscopy (Dover, New York, 1995).
  19. J. Tellinghuisen, J. Chem. Phys. 115, 10417 (2001).
  20. J. Tellinghuisen, J. Chem. Phys. 118, 1573 (2003).
  21. I. U. Goldschleger, V. Senekerimyan, M. S. Krage, H. Seferyan, K. C. Janda, and V. A. Apkarian, J. Chem. Phys. 124, 204507 (2006).
  22. M. S. Krage, M.S. thesis, University of California, 2006.
  23. M. Macler and M. C. Heaven, Chem. Phys. 151, 219 (1991).
  24. M. Macler, M. Erickson, H. S. Lin, and M. C. Heaven, J. Phys. Chem. 96, 4301 (1992).
  25. S. P. McGlynn, M. Kasha, and T. Azumi, J. Chem. Phys. 40, 507 (1964).
  26. D. Marić and J. P. Burrows, J. Phys. Chem. 100, 8645 (1996).
  27. R. I. Gray, K. M. Luckett, and J. Tellinghuisen, J. Phys. Chem. A 105, 11183 (2001).
  28. D. J. Tannor, Introduction To Quantum Mechanics: A Time-Dependent Perspective (University Science Books, Sausalito, 2007).
  29. M. Ovchinnikov and V. A. Apkarian, J. Chem. Phys. 106, 5775 (1997).
  30. P. F. Bernath, Spectra of Atoms and Molecules (Oxford University Press, New York, 1995).
  31. D. S. Kliger, J. W. Lewis, and C. E. Randall, Polarized Light in Optics and Spectroscopy (Academic, Boston, 1990).
  32. S. Mukamel, Principles of Nonlinear Optical Spectroscopy (Oxford University Press, New York, 1995).
  33. E. J. Heller, R. L. Sundberg, and D. Tannor, J. Phys. Chem. 86, 1822 (1982).
  34. L. Landau and E. Teller, Phys. Z. Sowjetunion 10, 34 (1936).
  35. E. E. Nikitin and J. Troe, Phys. Chem. Chem. Phys. 10, 1483 (2008).
  36. I. V. Alexandrov, Z. V. Nesterova, and V. O. Arkhirejev, Proc. SPIE 2700, 489 (1996).
  37. S. F. Fischer and S. Laubereau, Chem. Phys. Lett. 35, 6 (1975).
  38. A. Lauberea, Chem. Phys. Lett. 27, 600 (1974).
  39. D. J. Diestler and J. Manz, Mol. Phys. 33, 227 (1977).
  40. D. J. Diestler, J. Chem. Phys. 60, 2692 (1974).
  41. M. Karavitis, T. Kumada, I. Goldschleger, and V. Apkarian, Phys. Chem. Chem. Phys. 7, 791 (2005).
  42. M. Shugard, J. C. Tully, and A. Nitzan, J. Chem. Phys. 69, 336 (1978).
  43. M. Misawa, J. Chem. Phys. 90, 6563 (1989).
  44. M. Misawa, J. Chem. Phys. 91, 2575 (1989).
  45. V. Senekerimyan, I. Goldschleger, and V. Apkarian, J. Chem. Phys. 127, 214511 (2007).
  46. G. C. Pimental and S. W. Charles, Pure Appl. Chem. 7, 111 (1963).
  47. S. Subramanian and E. D. Sloan, J. Phys. Chem. B 106, 4348 (2002).
  48. W. F. Howard, Jr. and L. Andrews, J. Raman Spectrosc. 2, 447 (1974).
  49. E. W. Knapp, Chem. Phys. Lett. 58, 221 (1978).
  50. R. Englman, Non-Radiative Decay of Ions and Molecules in Solids (North-Holland, Amsterdam, 1979).
  51. D. J. Diestler, Chem. Phys. 7, 349 (1975).
  52. D. Schwarzer, J. Troe, M. Votsmeier, and M. Zerezke, J. Chem. Phys. 105, 3121 (1996).
  53. K. F. Herzfeld and T. A. Litovitz, Absorption and Dispersion of Ultrasonic Waves (Academic, New York, 1959).
  54. R. M. Stratt, Acc. Chem. Res. 28, 201 (1995).
  55. Q. Shi and E. Geva, J. Phys. Chem. A 107, 9059 (2003).

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