OSA's Digital Library

Optics Express

Optics Express

  • Editor: Andrew M. Weiner
  • Vol. 21, Iss. 22 — Nov. 4, 2013
  • pp: 26150–26161

Resonance enhanced Raman scatter in liquid benzene at vapor-phase absorption peaks

Adam Willitsford, C. Todd Chadwick, Hans Hallen, Stewart Kurtz, and C. Russell Philbrick  »View Author Affiliations


Optics Express, Vol. 21, Issue 22, pp. 26150-26161 (2013)
http://dx.doi.org/10.1364/OE.21.026150


View Full Text Article

Enhanced HTML    Acrobat PDF (1678 KB)





Browse Journals / Lookup Meetings

Browse by Journal and Year


   


Lookup Conference Papers

Close Browse Journals / Lookup Meetings

Article Tools

Share
Citations

Abstract

The resonance enhanced Raman spectra in the 1B2u mode of the forbidden benzene electronic transition band, ~230-270 nm, has been investigated. Resonance enhanced Raman scattering in both liquid benzene and liquid toluene exhibit the greatest enhancement when the wavelength of excitation is tuned to the vapor-phase absorption peaks; even though the sample volume is in a liquid state. Raman signals for the symmetric breathing mode of the carbon ring are found to be resonantly enhanced by several orders of magnitude (>500X) with deep UV excitation compared to non-resonant visible excitation. Since the benzene absorbs near this resonant wavelength, its effect on the sampled volume cannot be neglected in determining the resonance gain, as we discuss in detail. Large resonant gains correspond with excitation at the 247, 253, and 259 nm absorption peaks in the benzene vapor spectrum. The narrow region of resonance gain is investigated in detail around the absorption peak located at 259 nm using 0.25 nm steps in the excitation wavelength. We observe the resonance gain tracking the vapor phase absorption peaks and valleys within this narrow range. Results are interpreted in terms of the coherence forced by the use of a forbidden transition for resonance excitation.

© 2013 Optical Society of America

OCIS Codes
(040.7190) Detectors : Ultraviolet
(260.2510) Physical optics : Fluorescence
(260.5740) Physical optics : Resonance
(290.5860) Scattering : Scattering, Raman
(300.0300) Spectroscopy : Spectroscopy
(300.1030) Spectroscopy : Absorption

ToC Category:
Spectroscopy

History
Original Manuscript: August 27, 2013
Revised Manuscript: October 6, 2013
Manuscript Accepted: October 9, 2013
Published: October 24, 2013

Citation
Adam Willitsford, C. Todd Chadwick, Hans Hallen, Stewart Kurtz, and C. Russell Philbrick, "Resonance enhanced Raman scatter in liquid benzene at vapor-phase absorption peaks," Opt. Express 21, 26150-26161 (2013)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-21-22-26150


Sort:  Author  |  Year  |  Journal  |  Reset  

References

  1. L. Ziegler and B. Hudson, “Resonance Raman scattering of benzene and benzene-d6 with 212.8 nm excitation,” J. Chem. Phys.74(2), 982–992 (1981). [CrossRef]
  2. S. Asher and C. Johnson, “Resonance Raman excitation profile through the 1B2u state of benzene,” J. Phys. Chem.89(8), 1375–1379 (1985). [CrossRef]
  3. D. Gerrity, L. Ziegler, P. Kelly, R. Desiderio, and B. Hudson, “Ultraviolet resonance Raman spectroscopy of benzene vapor with 220-184 nm excitation,” J. Chem. Phys.83(7), 3209–3213 (1985). [CrossRef]
  4. R. Sension, R. Brudzynski, S. Li, B. Hudson, F. Zerbetto, and M. Z. Zgierski, “Resonance Raman spectroscopy of the B1u region of benzene: analysis in terms of pseudo-Jahn-Teller Distortion,” J. Chem. Phys.96(4), 2617–2628 (1992). [CrossRef]
  5. R. Sension, R. Brudzynski, and B. Hudson, “Vacuum ultraviolet resonance Raman studies of the valence electronic states of benzene and benzene-d6: The E1u state and a putative A2u state,” J. Chem. Phys.94(2), 873–882 (1991). [CrossRef]
  6. L. Ziegler and A. Albrecht, “Raman scattering of benzene in the ultraviolet,” J. Chem. Phys.67(6), 2753–2757 (1977). [CrossRef]
  7. G. Korenowski, L. Ziegler, and A. Albrecht, “Calculations of resonance Raman cross sections in forbidden electronic transitions: scattering of the 992 cm−1 mode in the 1B2u band of benzene,” J. Chem. Phys.68(3), 1248–1252 (1978). [CrossRef]
  8. A. Albrecht and M. Hutley, “On the dependence of vibrational Raman intensity on the wavelength of incident light,” J. Chem. Phys.55(9), 4438–4443 (1971). [CrossRef]
  9. C. R. Philbrick, D. M. Brown, A. H. Willitsford, P. S. Edwards, A. M. Wyant, Z. Z. Liu, C. T. Chadwick, and H. Hallen, “Remote sensing of chemical species in the atmosphere,” Proc. 4th Lidar Atmos. Appl. 89th AMS, 2009 http://ams.confex.com/ams/pdfpapers/150051.pdf
  10. A. Sedlacek and C. Chen, “Exploitation of resonance Raman spectroscopy as a remote chemical sensor,” BNL-61359: Conf. 950787–35 (1995).
  11. A. Sedlacek and C. Chen, “Remote detection of trace effluents using resonance Raman spectroscopy,” BNL-49542: Conf. 9311173–2 (1995).
  12. C. Chen, D. Heglund, M. Ray, D. Harder, R. Dobert, K. Leung, M. Wu, and A. Sedlacek, “Application of resonance Raman lidar for chemical species identification,” BNL-64388: Conf.-970465–19 (1997).
  13. C. L. Jahncke, H. D. Hallen, and M. A. Paesler, “Nano-Raman spectroscopy and imaging with the near-field scanning optical microscope,” J. Raman Spectrosc.27(8), 579–586 (1996). [CrossRef]
  14. H. D. Hallen, “Nano-Raman spectroscopy: surface plasmon emission, field gradients, and fundamentally near field propagation effects,” NanoBiotechnology3(3), 197 (2009), doi:. [CrossRef]
  15. A. Willitsford, C. T. Chadwick, H. Hallen, and C. R. Philbrick, “Resonance Raman measurements utilizing a tunable deep UV source,” Proc. SPIE6950, 695010 (2008). [CrossRef]
  16. A. Willitsford, Resonance Raman Spectroscopy in the Ultraviolet using a Tunable Laser, Ph.D. Dissertation, Penn State University (2008) https://etda.libraries.psu.edu/paper/8149/ .
  17. C. T. Chadwick, Resonance Raman Spectroscopy Utilizing Tunable Deep Ultraviolet Excitation for Materials Characterization, Ph.D. Dissertation, N. C. State University (2009) http://www.lib.ncsu.edu/resolver/1840.16/5473 .
  18. S. Asher, C. Johnson, and J. Murtaugh, “Development of a new UV resonance Raman spectrometer for the 217-400 nm spectral region,” Rev. Sci. Instrum.54(12), 1657–1662 (1983). [CrossRef]
  19. S. Asher, Coal Liquefaction Process Streams Characterization and Evaluation UV Resonance Raman Studies of Coal Liquid Residuals. DOE/PC/89883–67 (DE93009669) DOE (1993).
  20. American Petroleum Institute Research Project 44, Selected Ultraviolet Spectral Data2 (1945–1984), Thermodynamics Research Center, Department of Chemical Engineering, Texas A & M University http://catalog.lib.ncsu.edu/record/NCSU623743 .
  21. J. M. Dixon, M. Taniguchi, and J. S. Lindsey, “PhotochemCAD 2: A refined program with accompanying spectral databases for photochemical calculations,” Photochem. Photobiol. 81, 212–213 (2005) http://omlc.ogi.edu/spectra/PhotochemCAD/html/042.html (benzene) http://omlc.ogi.edu/spectra/PhotochemCAD/html/090.html (toluene). [CrossRef]
  22. T. Etzkorn, B. Klotz, S. Sørensen, I. V. Patroescu, I. Barnes, K. H. Becker, and U. Platt, “Gas-phase absorption cross sections of 24 monocyclic aromatic hydrocarbons in the UV and IR spectral ranges,” Atmos. Environ.33(4), 525–540 (1999) (MPI-Mainz-UV-VIS Spectral Atlas of Gaseous Molecules http://www.satellite.mpic.de/spectral_atlas.org). [CrossRef]
  23. K. G. Spears and S. A. Rice, “Study of the lifetimes of individual vibronic states of the isolated benzene molecule,” J. Chem. Phys.55(12), 5561–5581 (1971). [CrossRef]
  24. J. H. Callomon, T. M. Dunn, and I. M. Mills, ““Rotational analysis of the 2600 Å absorption of benzene,” Philos. Trans. R. Soc. London, Ser. A259(1104), 499–532 (1966).
  25. E. B. Wilson, “The normal modes and frequencies of vibration of the regular plane hexagon model of the benzene molecule,” Phys. Rev.45(10), 706–714 (1934). [CrossRef]
  26. T. C. Strekas, D. H. Adams, A. Packer, and T. G. Spiro, “Absorption corrections and concentration optimization for absorbing samples in resonance Raman spectroscopy,” Appl. Spectrosc.28(4), 324–327 (1974). [CrossRef]
  27. H. Inaba, “Chapter 5: Detection of atoms and molecules by Raman scattering and resonance fluorescence,” in Laser Monitoring of the Atmosphere, E. D. Hinkley, ed. Springer-Verlag, (1976).
  28. P. G. Harmon and S. A. Asher, “Environmental dependence of preresonance Raman crosssection dispersions: Benzene vaporphase excitation profiles,” J. Chem. Phys.93(5), 3094 (1990). [CrossRef]
  29. A. H. Willitsford, Johns Hopkins University - Applied Physics Lab, Laurel, MD 20709, and C. T. Chadwick, S. Kurtz, H. D. Hallen, C. R. Philbrick, are preparing a manuscript to be called “Resonance enhanced Raman scattering of the υ9 and υ10 b2u vibrational modes in the 1B2u absorption band.”
  30. D. R. Falcone, D. C. Douglass, and D. W. McCall, “Self-diffusion in benzene,” J. Phys. Chem.71(8), 2754–2755 (1967). [CrossRef]

Cited By

Alert me when this paper is cited

OSA is able to provide readers links to articles that cite this paper by participating in CrossRef's Cited-By Linking service. CrossRef includes content from more than 3000 publishers and societies. In addition to listing OSA journal articles that cite this paper, citing articles from other participating publishers will also be listed.


« Previous Article  |  Next Article »

OSA is a member of CrossRef.

CrossCheck Deposited