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Lineshape of rotational spectrum of CO in 4He droplets

J. Chem. Phys. 128, 094303 (2008); doi:10.1063/1.2833979

Published 3 March 2008

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Robert E. Zillich,1,2 K. Birgitta Whaley,3,4 and Klaus von Haeften5
1Fraunhofer ITWM, 67663 Kaiserslautern, Germany
2Institut für Theoretische Physik, Johannes Kepler Universität, A-4040 Linz, Austria
3Department of Chemistry, University of California, Berkeley, California 94720, USA
4Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720, USA
5Department of Physics and Astronomy, University of Leicester, Leicester LE1 7RH, United Kingdom
In a recent experiment the rovibrational spectrum of CO isotopomers in superfluid helium-4 droplets was measured, and a Lorentzian lineshape with a large line width of 0.024  K (half width at half maximum) was observed [von Haeften et al., Phys. Rev. B 73, 054502 (2006)]. In the accompanying theoretical analysis it was concluded that the broadening mechanism may be homogeneous and due to coupling to collective droplet excitations (phonons). Here we generalize the lineshape analysis to account for the statistical distribution of droplet sizes present in nozzle expansion experiments. These calculations suggest an alternative explanation for the spectral broadening, namely, that the coupling to phonons can give rise to an inhomogeneous broadening as a result of averaging isolated rotation-phonon resonances over a broad cluster size distribution. This is seen to result in Lorentzian lineshapes, with a width and peak position that depend weakly on the size distribution, showing oscillatory behavior for the narrower size distributions. These oscillations decrease with droplet size and for large enough droplets (~104) the line widths saturate at a value equal to the homogeneous line width calculated for the bulk limit. ©2008 American Institute of Physics
History: Received 17 August 2006; accepted 18 December 2007; published 3 March 2008
Permalink: http://link.aip.org/link/?JCPSA6/128/094303/1
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KEYWORDS and PACS

Keywords
PACS
  • 63.50.-x
    Vibrational states in disordered systems
  • 61.20.Ja
    Computer simulation of liquid structure
  • YEAR: 2008

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (42)
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  1. C. Callegari, K. K. Lehmann, R. Schmied, and G. Scoles, J. Chem. Phys. 115, 10090 (2001).
  2. F. Paesani, A. Viel, F. A. Gianturco, and K. B. Whaley, Phys. Rev. Lett. 90, 073401 (2003).
  3. S. Moroni, A. Sarsa, S. Fantoni, K. E. Schmidt, and S. Baroni, Phys. Rev. Lett. 90, 143401 (2003).
  4. N. Blinov, X. Song, and P. Roy, J. Chem. Phys. 120, 5916 (2004).
  5. R. E. Zillich, F. Paesani, Y. Kwon, and K. B. Whaley, J. Chem. Phys. 123, 114301 (2005).
  6. Y. Kwon and K. B. Whaley, Phys. Rev. Lett. 83, 4108 (1999).
  7. Y. Kwon, P. Huang, M. V. Patel, D. Blume, and K. B. Whaley, J. Chem. Phys. 113, 6469 (2000).
  8. C. Callegari, A. Conjusteau, I. Reinhard, K. K. Lehmann, G. Scoles, and F. Dalfovo, Phys. Rev. Lett. 83, 5058 (1999).
    9. See also C. Callegari, A. Conjusteau, I. Reinhard, K. K. Lehmann, G. Scoles, and F. Dalfovo, ibid. 84, 1848(E) (2000).
  9. V. S. Babichenko and Yu. Kagan, Phys. Rev. Lett. 83, 3458 (1999).
  10. R. Zillich, Y. Kwon, and K. B. Whaley, Phys. Rev. Lett. 93, 250401 (2004).
  11. S. Grebenev, M. Havenith, F. Madeja, J. P. Toennies, and A. F. Vilesov, J. Chem. Phys. 113, 9060 (2000).
  12. K. Nauta and R. E. Miller, Phys. Rev. Lett. 82, 4480 (1999).
  13. A. Conjusteau, C. Callegari, I. Reinhard, K. K. Lehmann, and G. Scoles, J. Chem. Phys. 113, 4840 (2000).
  14. M. Hartmann, N. Pörtner, B. Sartakov, J. P. Toennies, and A. F. Vilesov, J. Chem. Phys. 110, 5109 (1999).
  15. K. von Haeften, S. Rudolph, I. Simanovski, M. Havenith, R. Zillich, and K. B. Whaley, Phys. Rev. B 73, 054502 (2006).
  16. K. Nauta and R. E. Miller, J. Chem. Phys. 113, 9466 (2000).
  17. K. von Haeften, S. Rudolph, A. Metzelthin, I. Simanovski, A. Ruediger, C. Krause, and M. Havenith, Phys. Rev. Lett. 95, 215301 (2005).
  18. K. Nauta and R. E. Miller, J. Chem. Phys. 113, 10158 (2000).
  19. K. Nauta and R. E. Miller, J. Chem. Phys. 115, 8384 (2001).
  20. A. M. Stoneham, Rev. Mod. Phys. 41, 82 (1969).
  21. D. L. Orth, R. J. Mashl, and J. L. Skinner, J. Phys.: Condens. Matter 5, 2533 (1993).
  22. A. Abragam, Principles of Nuclear Magnetism, International Series of Monographs on Physics (Oxford University Press, New York, 1983).
  23. C. Callegari, K. K. Lehmann, R. Schmied, and G. Scoles, J. Chem. Phys. 115, 10090 (2001).
  24. R. Zillich and K. B. Whaley, Phys. Rev. B 6, 104517 (2004).
  25. K. K. Lehmann, Mol. Phys. 97, 645 (1999).
  26. S. Grebenev, M. Hartmann, M. Havenith, B. Sartakov, J. P. Toennies, and A. F. Vilesov, J. Chem. Phys. 112, 4485 (2000).
  27. B. Dick and A. Slenczka, J. Chem. Phys. 115, 10206 (2001).
  28. A. R. W. McKellar, J. Chem. Phys. 125, 164328 (2006).
  29. T. Skrbic, S. Moroni, and S. Baroni, J. Phys. Chem. A 111, 7640 (2007).
  30. K. K. Lehmann, J. Chem. Phys. 126, 024108 (2007).
  31. D. R. Tilley and J. Tilley, Superfluidity and Superconductivity (Hilger, Bristol, UK, 1986).
  32. M. Bixon and J. Jortner, J. Chem. Phys. 48, 715 (1968).
  33. I. Reinhard, C. Callegari, A. Conjusteau, K. K. Lehmann, and G. Scoles, Phys. Rev. Lett. 82, 5036 (1999).
  34. J. M. Merritt, G. E. Douberly, and R. E. Miller, J. Chem. Phys. 121, 1309 (2004).
  35. E. Krotscheck, M. Saarela, and J. Epstein, Phys. Rev. B 38, 111 (1988).
  36. B. E. Clements, E. Krotscheck, and M. Saarela, Phys. Rev. B 55, 5959 (1997).
  37. E. Krotscheck and R. Zillich, Phys. Rev. B 58, 5707 (1998).
  38. E. Krotscheck and R. Zillich, J. Chem. Phys. 115, 10161 (2001).
  39. E. Krotscheck, M. Saarela, K. Schörkhuber, and R. Zillich, Phys. Rev. Lett. 80, 4709 (1998).
  40. A. R. W. McKellar, Yunjie Xu, and W. Jäger, Phys. Rev. Lett. 97, 183401 (2006).
  41. A. R. W. McKellar, J. Chem. Phys. 127, 044315 (2007).
  42. The width for the [overline N]=2600 spectrum shown here is 0.022  K, somewhat less than the value of 0.024  K reported in Ref. 15 that was derived by averaging over many tens of such individual spectra.

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