Abstract

We report the detection of characteristic Raman lines for several chemicals using a single-beam coherent anti-Stokes Raman scattering (CARS) technique from a 12 meter standoff distance. Single laser shot spectra are obtained with sufficient signal to noise ratio to allow molecular identification. Background and spectroscopic discrimination are achieved through binary phase pulse shaping for optimal excitation of a single vibrational mode. These results provide a promising approach to standoff detection of chemicals, hazardous contaminants, and explosives.

© 2008 Optical Society of America

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References

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  1. M. Gruebele, G. Roberts, M. Dantus, R. M. Bowman, and A. H. Zewail, "Femtosecond temporal spectroscopy and direct inversion to the potential - application to iodine," Chem. Phys. Lett. 166, 459-469 (1990).
    [CrossRef]
  2. A. M. Weiner, D. E. Leaird, G. P. Wiederrecht, and K. A. Nelson, "Femtosecond pulse sequences used for optical manipulation of molecular-motion," Science 247, 1317-1319 (1990).
    [CrossRef] [PubMed]
  3. N. Dudovich, D. Oron, and Y. Silberberg, "Single-pulse coherently controlled nonlinear Raman spectroscopy and microscopy," Nature 418, 512-514 (2002).
    [CrossRef] [PubMed]
  4. D. Oron, N. Dudovich, and Y. Silberberg, "Femtosecond phase-and-polarization control for background-free coherent anti-Stokes Raman spectroscopy," Phys. Rev. Lett. 90, 213902 (2003).
    [CrossRef] [PubMed]
  5. S. H. Lim, A. G. Caster, and S. R. Leone, "Single-pulse phase-control interferometric coherent anti-Stokes Raman scattering spectroscopy," Phys. Rev. A 72, 0418031-0418034 (2005).
    [CrossRef]
  6. B. von Vacano and M. Motzkus, "Time-resolved two color single-beam CARS employing supercontinuum and femtosecond pulse shaping," Opt. Commun. 264, 488-493 (2006).
    [CrossRef]
  7. M. O. Scully, G. W. Kattawar, R. P. Lucht, T. Opatrny, H. Pilloff, A. Rebane, A. V. Sokolov, and M. S. Zubairy, "FAST CARS: Engineering a laser spectroscopic technique for rapid identification of bacterial spores," P. Natl. Acad. Sci. USA 99, 10994-11001 (2002).
    [CrossRef]
  8. D. Pestov, R. K. Murawski, G. O. Ariunbold, X. Wang, M. C. Zhi, A. V. Sokolov, V. A. Sautenkov, Y. V. Rostovtsev, A. Dogariu, Y. Huang, and M. O. Scully, "Optimizing the laser-pulse configuration for coherent Raman spectroscopy," Science 316, 265-268 (2007).
    [CrossRef] [PubMed]
  9. M. Nisoli, S. DeSilvestri, and O. Svelto, "Generation of high energy 10 fs pulses by a new pulse compression technique," Appl. Phys. Lett. 68, 2793-2795 (1996).
    [CrossRef]
  10. L. Gallmann, T. Pfeifer, P. M. Nagel, M. J. Abel, D. M. Neumark, and S. R. Leone, "Comparison of the filamentation and the hollow-core fiber characteristics for pulse compression into the few-cycle regime," App. Phys. B 86, 561-566 (2007).
    [CrossRef]
  11. V. V. Lozovoy, I. Pastirk, and M. Dantus, "Multiphoton intrapulse interference. 4. Characterization of the phase of ultrashort laser pulses," Opt. Lett. 29, 775-777 (2004).
    [CrossRef] [PubMed]
  12. B. Xu, J. M. Gunn, J. M. Dela Cruz, V. V. Lozovoy, and M. Dantus, "Quantitative investigation of the multiphoton intrapulse interference phase scan method for simultaneous phase measurement and compensation of femtosecond laser pulses," J. Opt. Soc. Am. B 23, 750-759 (2006).
    [CrossRef]
  13. I. Pastirk, X. Zhu, R. M. Martin, and M. Dantus, "Remote characterization and dispersion compensation of amplified shaped femtosecond pulses using MIIPS," Opt. Express 14, 8885-8889 (2006).
    [CrossRef] [PubMed]
  14. D. Oron, N. Dudovich, and Y. Silberberg, "Single-pulse phase-contrast nonlinear Raman spectroscopy," Phys. Rev. Lett. 89, 273001 (2002).
    [CrossRef]
  15. M. Comstock, V. V. Lozovoy, I. Pastirk, and M. Dantus, "Multiphoton intrapulse interference 6; binary phase shaping," Opt. Express 12, 1061-1066 (2004).
    [CrossRef] [PubMed]
  16. V. V. Lozovoy, B. W. Xu, J. C. Shane, and M. Dantus, "Selective nonlinear optical excitation with pulses shaped by pseudorandom Galois fields," Phys. Rev. A 74, 0418051-0418054 (2006).
    [CrossRef]
  17. M. R. Schroeder, Number Theory in Science and Communication: With Applications in Cryptography, Physics, Digital Information, Computing, and Self-similarity (Springer, Berlin, 1997), p. 362.
  18. J. Knauer, "Merit factors for least autocorrelation binary sequences," retrieved http://www.chemistry.msu.edu/faculty/dantus/merit_factor_records.html.
  19. A. M. Weiner, J. P. Heritage, and E. M. Kirschner, "High-resolution femtosecond pulse shaping," J. Opt. Soc. Am. B 5, 1563-1572 (1988).
    [CrossRef]
  20. G. Varsanyi, Vibrational Spectra of Benzene Derivatives (Academic Press, New York, 1969).
  21. J. Konradi, A. K. Singh, and A. Materny, "Selective excitation of molecular modes in a mixture by optimal control of electronically nonresonant femtosecond four-wave mixing spectroscopy," J. Photochem. Photobiol. 180, 289-299 (2006).
    [CrossRef]
  22. This work was first presented at the CLEO/QELS conference, May 6-11, 2007.

2007 (2)

D. Pestov, R. K. Murawski, G. O. Ariunbold, X. Wang, M. C. Zhi, A. V. Sokolov, V. A. Sautenkov, Y. V. Rostovtsev, A. Dogariu, Y. Huang, and M. O. Scully, "Optimizing the laser-pulse configuration for coherent Raman spectroscopy," Science 316, 265-268 (2007).
[CrossRef] [PubMed]

L. Gallmann, T. Pfeifer, P. M. Nagel, M. J. Abel, D. M. Neumark, and S. R. Leone, "Comparison of the filamentation and the hollow-core fiber characteristics for pulse compression into the few-cycle regime," App. Phys. B 86, 561-566 (2007).
[CrossRef]

2006 (5)

V. V. Lozovoy, B. W. Xu, J. C. Shane, and M. Dantus, "Selective nonlinear optical excitation with pulses shaped by pseudorandom Galois fields," Phys. Rev. A 74, 0418051-0418054 (2006).
[CrossRef]

J. Konradi, A. K. Singh, and A. Materny, "Selective excitation of molecular modes in a mixture by optimal control of electronically nonresonant femtosecond four-wave mixing spectroscopy," J. Photochem. Photobiol. 180, 289-299 (2006).
[CrossRef]

B. Xu, J. M. Gunn, J. M. Dela Cruz, V. V. Lozovoy, and M. Dantus, "Quantitative investigation of the multiphoton intrapulse interference phase scan method for simultaneous phase measurement and compensation of femtosecond laser pulses," J. Opt. Soc. Am. B 23, 750-759 (2006).
[CrossRef]

I. Pastirk, X. Zhu, R. M. Martin, and M. Dantus, "Remote characterization and dispersion compensation of amplified shaped femtosecond pulses using MIIPS," Opt. Express 14, 8885-8889 (2006).
[CrossRef] [PubMed]

B. von Vacano and M. Motzkus, "Time-resolved two color single-beam CARS employing supercontinuum and femtosecond pulse shaping," Opt. Commun. 264, 488-493 (2006).
[CrossRef]

2005 (1)

S. H. Lim, A. G. Caster, and S. R. Leone, "Single-pulse phase-control interferometric coherent anti-Stokes Raman scattering spectroscopy," Phys. Rev. A 72, 0418031-0418034 (2005).
[CrossRef]

2004 (2)

2003 (1)

D. Oron, N. Dudovich, and Y. Silberberg, "Femtosecond phase-and-polarization control for background-free coherent anti-Stokes Raman spectroscopy," Phys. Rev. Lett. 90, 213902 (2003).
[CrossRef] [PubMed]

2002 (3)

N. Dudovich, D. Oron, and Y. Silberberg, "Single-pulse coherently controlled nonlinear Raman spectroscopy and microscopy," Nature 418, 512-514 (2002).
[CrossRef] [PubMed]

M. O. Scully, G. W. Kattawar, R. P. Lucht, T. Opatrny, H. Pilloff, A. Rebane, A. V. Sokolov, and M. S. Zubairy, "FAST CARS: Engineering a laser spectroscopic technique for rapid identification of bacterial spores," P. Natl. Acad. Sci. USA 99, 10994-11001 (2002).
[CrossRef]

D. Oron, N. Dudovich, and Y. Silberberg, "Single-pulse phase-contrast nonlinear Raman spectroscopy," Phys. Rev. Lett. 89, 273001 (2002).
[CrossRef]

1996 (1)

M. Nisoli, S. DeSilvestri, and O. Svelto, "Generation of high energy 10 fs pulses by a new pulse compression technique," Appl. Phys. Lett. 68, 2793-2795 (1996).
[CrossRef]

1990 (2)

M. Gruebele, G. Roberts, M. Dantus, R. M. Bowman, and A. H. Zewail, "Femtosecond temporal spectroscopy and direct inversion to the potential - application to iodine," Chem. Phys. Lett. 166, 459-469 (1990).
[CrossRef]

A. M. Weiner, D. E. Leaird, G. P. Wiederrecht, and K. A. Nelson, "Femtosecond pulse sequences used for optical manipulation of molecular-motion," Science 247, 1317-1319 (1990).
[CrossRef] [PubMed]

1988 (1)

App. Phys. B (1)

L. Gallmann, T. Pfeifer, P. M. Nagel, M. J. Abel, D. M. Neumark, and S. R. Leone, "Comparison of the filamentation and the hollow-core fiber characteristics for pulse compression into the few-cycle regime," App. Phys. B 86, 561-566 (2007).
[CrossRef]

Appl. Phys. Lett. (1)

M. Nisoli, S. DeSilvestri, and O. Svelto, "Generation of high energy 10 fs pulses by a new pulse compression technique," Appl. Phys. Lett. 68, 2793-2795 (1996).
[CrossRef]

Chem. Phys. Lett. (1)

M. Gruebele, G. Roberts, M. Dantus, R. M. Bowman, and A. H. Zewail, "Femtosecond temporal spectroscopy and direct inversion to the potential - application to iodine," Chem. Phys. Lett. 166, 459-469 (1990).
[CrossRef]

J. Opt. Soc. Am. B (2)

J. Photochem. Photobiol. (1)

J. Konradi, A. K. Singh, and A. Materny, "Selective excitation of molecular modes in a mixture by optimal control of electronically nonresonant femtosecond four-wave mixing spectroscopy," J. Photochem. Photobiol. 180, 289-299 (2006).
[CrossRef]

Nature (1)

N. Dudovich, D. Oron, and Y. Silberberg, "Single-pulse coherently controlled nonlinear Raman spectroscopy and microscopy," Nature 418, 512-514 (2002).
[CrossRef] [PubMed]

Opt. Commun. (1)

B. von Vacano and M. Motzkus, "Time-resolved two color single-beam CARS employing supercontinuum and femtosecond pulse shaping," Opt. Commun. 264, 488-493 (2006).
[CrossRef]

Opt. Express (2)

Opt. Lett. (1)

P. Natl. Acad. Sci. USA (1)

M. O. Scully, G. W. Kattawar, R. P. Lucht, T. Opatrny, H. Pilloff, A. Rebane, A. V. Sokolov, and M. S. Zubairy, "FAST CARS: Engineering a laser spectroscopic technique for rapid identification of bacterial spores," P. Natl. Acad. Sci. USA 99, 10994-11001 (2002).
[CrossRef]

Phys. Rev. A (2)

S. H. Lim, A. G. Caster, and S. R. Leone, "Single-pulse phase-control interferometric coherent anti-Stokes Raman scattering spectroscopy," Phys. Rev. A 72, 0418031-0418034 (2005).
[CrossRef]

V. V. Lozovoy, B. W. Xu, J. C. Shane, and M. Dantus, "Selective nonlinear optical excitation with pulses shaped by pseudorandom Galois fields," Phys. Rev. A 74, 0418051-0418054 (2006).
[CrossRef]

Phys. Rev. Lett. (2)

D. Oron, N. Dudovich, and Y. Silberberg, "Single-pulse phase-contrast nonlinear Raman spectroscopy," Phys. Rev. Lett. 89, 273001 (2002).
[CrossRef]

D. Oron, N. Dudovich, and Y. Silberberg, "Femtosecond phase-and-polarization control for background-free coherent anti-Stokes Raman spectroscopy," Phys. Rev. Lett. 90, 213902 (2003).
[CrossRef] [PubMed]

Science (2)

A. M. Weiner, D. E. Leaird, G. P. Wiederrecht, and K. A. Nelson, "Femtosecond pulse sequences used for optical manipulation of molecular-motion," Science 247, 1317-1319 (1990).
[CrossRef] [PubMed]

D. Pestov, R. K. Murawski, G. O. Ariunbold, X. Wang, M. C. Zhi, A. V. Sokolov, V. A. Sautenkov, Y. V. Rostovtsev, A. Dogariu, Y. Huang, and M. O. Scully, "Optimizing the laser-pulse configuration for coherent Raman spectroscopy," Science 316, 265-268 (2007).
[CrossRef] [PubMed]

Other (4)

M. R. Schroeder, Number Theory in Science and Communication: With Applications in Cryptography, Physics, Digital Information, Computing, and Self-similarity (Springer, Berlin, 1997), p. 362.

J. Knauer, "Merit factors for least autocorrelation binary sequences," retrieved http://www.chemistry.msu.edu/faculty/dantus/merit_factor_records.html.

This work was first presented at the CLEO/QELS conference, May 6-11, 2007.

G. Varsanyi, Vibrational Spectra of Benzene Derivatives (Academic Press, New York, 1969).

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Figures (5)

Fig. 1.
Fig. 1.

(a) Supercontinuum spectrum (red) and the phase measured using MIIPS (magenta). (b) Measured SHG spectra (blue) from the compensated pulses (spectrometer limited at 300 nm). The experimental SHG spectrum has a bandwidth of 73nm (FWHM), which agrees well with simulations for transform-limited pulses based on the measured spectrum. The supercontinuum pulses were compressed to 4.8 fs by MIIPS phase compensation (see inset). (c) Residual phase on the laser after compensation.

Fig.2.
Fig.2.

Setup and performance of the single-beam CARS. (a) The experimental setup. (b) The spectrum, phase and polarization of components of the shaped laser pulse. The pump and Stokes (red) components have vertical polarization (y) while the probe (green) and CARS signal (blue) have horizontal polarization (x). The inset shows a diagram for the CARS process. (c) Spectra of six consecutive single shot spectra of toluene collected at a standoff 12 m distance.

Fig. 3.
Fig. 3.

Single-beam CARS spectra from liquid, gaseous and solid state samples. (a) CARS spectra from liquid toluene, o-nitrotoluene and m-nitrotoluene; (b) CARS spectra from liquid ortho, meta and para-xylene. (c) CARS spectra from CS2, CH2Cl2 and CHCl3 vapors; (d) CARS spectra from solid polycarbonate, polystyrene and PMMA.

Fig. 4.
Fig. 4.

Single-beam CARS illustration of sensitivity and discrimination against background signals. (a) Unprocessed spectra of m-xylene collected at a standoff 12 m distance with (black) and without (red) phase distortion compensation using MIIPS; note the presence of a large non-resonant contribution (compared to the resonant signal) in both cases. (b) The red phase is designed to optimize excitation of the ν1 breathing mode at 725 cm-1 and the blue phase is designed to optimize excitation of ν12 in-plane bending mode at 1000 cm-1. The lower panel shows the calculated temporal profiles corresponding to red and blue phases. (c) Unprocessed CARS spectra from m-xylene with two specially designed binary phases. Note that the non-resonant contribution is successfully suppressed eliminating the need for data processing. The designed binary phases control the ratio between the two Raman peaks with an overall two order-of-magnitude discrimination from 7:1 to 1:12. (d) Integrated intensity for different binary phases (optimized for different Raman shifts) applied in the pulse shaper.

Fig. 5.
Fig. 5.

Single-beam CARS spectra with back scatter signal detection. (a) Unprocessed spectrum of o-xylene. (b) Processed spectra of o-xylene and toluene.

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