Abstract

Kinetic spectroscopy based on excimer-laser flash photolysis and color-center-laser (CCL) infrared probing is explored. In simple absorption, the achievable signal-to-noise ratio (S/N) is not satisfactory even though the signal itself (corresponding to >1% absorption) is fairly large. This is due to amplitude fluctuations of the CCL. By using a double-beam detection scheme to balance out these amplitude fluctuations the sensitivity can be improved to the extent that a 1% absorption gives a S/N ∼ 100. In certain situations transient decreases in absorption of the precursor and transient increases in absorption due to final product formation can produce severe interfering signals even in simple systems. This problem is overcome without a major loss in sensitivity by a recently developed 45° magnetic rotation scheme. These points are illustrated with spectra of Br, OH, and NH2.

© 1985 Optical Society of America

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  1. K. C. Herr and G. C. Pimentel, “A rapid-scan infrared spectrometer; flash photolytic detection of chloroformic acid and CF2,” Appl. Opt. 4, 25–30 (1965).
    [Crossref]
  2. D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
    [Crossref]
  3. K. C. Kim, M. J. Reisfeld, and W. B. Person, “Diode laser spectroscopy of the transient UF5 radical following laser photolysis of UF6,” J. Mol. Struct. 60, 205–213 (1980).
    [Crossref]
  4. G. A. Laguna and S. L. Baughcum, “Real-time detection of methyl radicals by diode laser absorption at 608 cm−1,” Chem. Phys. Lett. 88, 568–571 (1982).
    [Crossref]
  5. H. Petek, D. J. Nesbitt, P. R. Ogilby, and C. B. Moore, “Infrared flash kinetic spectroscopy: the ν1 and ν3 spectra of singlet methylene,” J. Phys. Chem. 87, 5367–5371 (1983).
    [Crossref]
  6. G. Litfin, R. F. Curl, C. R. Pollock, and F. K. Tittel, “Sensitivity enhancement of laser absorption spectroscopy by magnetic rotation effect,” J. Chem. Phys. 72, 6602–6605 (1980).
    [Crossref]
  7. C. S. Gudemann, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Tone-burst modulated color center laser spectroscopy,” Opt. Lett. 8, 310–315 (1983).
    [Crossref]
  8. H. Adams, J. L. Hall, R. F. Curl, J. V. V. Kasper, and F. K. Tittel, “Sensitivity improvement of tone-burst modulated spectroscopy with a color-center laser,” J. Opt. Soc Am. B 1, 710–714 (1984).
    [Crossref]
  9. C. S. Gudeman, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Velocity-modulated infrared spectroscopy of molecular ions: the ν1 band of HCO+,” Phys. Rev. Lett. 50, 727–731 (1983).
    [Crossref]
  10. E. D. Hinkley, R. T. Ku, and P. L. Kelley, in Laser Monitoring of the Atmosphere, E. D. Hinkley, ed. (Springer-Verlag, Berlin, 1976), Chap.6, p. 244.
  11. J. Hall, H. Adams, L. A. Russell, J. V. V. Kasper, F. K. Tittel, and R. F. Curl, “Kinetic spectroscopy with the color center laser,” in Proceedings of the International Conference on Lasers’83, R. C. Powell, ed. (STS, McLean, Va., 1985).
  12. J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Computer control of broadly tunable lasers: conversion of a color center laser into a high resolution spectrometer,” Appl. Opt. 21, 236–247 (1982).
    [Crossref] [PubMed]
  13. This data processing often included Savitzky–Golay numerical smoothing methods.A. Savitzky and M. J. E. Golay, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 36, 1627–1639 (1964);J. Steinier, Y. Ter-monia, and J. Deltour, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 44, 1906–1909 (1972).
    [Crossref] [PubMed]
  14. E. Luc-Koenig, C. Morrillon, and J. Verges, “Etude de la transition interdite 2P1/2 ← 2P3/2 de la configuration np5 dans le brome et l’iode par spectrometrie de Fourier,” Physica 70, 175–189 (1973).
    [Crossref]
  15. J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Observation of the 2P1/2 ← 2P3/2 transition of the Br atom by color center laser spectroscopy,” Chem. Phys. Lett. 77, 211–213 (1981).
    [Crossref]
  16. F. Magnotta, D. J. Nesbitt, and S. R. Leone, “Excimer laser flash photolysis studies of translational to vibrational energy transfer,” Chem. Phys. Lett. 83, 21–25 (1981).
    [Crossref]
  17. J. P. Maillard, J. Chauville, and A. W. Mantz, “High-resolution emission spectrum of OH in an oxyacetylene flame from 3.7 to 0.9 μm,” J. Mol. Spectrosc. 63, 120–141 (1976).
    [Crossref]
  18. J. Hall, H. Adams, J. V. V. Kasper, R. F. Curl, and F. K. Tittel, J. Opt. Soc. Am. B 2, 781–785 (1985).
    [Crossref]
  19. H. Adams, D. Reinert, P. Kalkert, and W. Urban, “A differential detection scheme for Faraday rotation spectroscopy with a color center laser,” Appl. Phys. B 34, 179–185 (1984).
    [Crossref]
  20. J. R. McNesby, I. Tanaka, and H. Okabe, “Vacuum ultraviolet photochemistry. III. Primary processes in the vacuum ultraviolet photolysis of water and ammonia,” J. Chem. Phys. 36, 605–607 (1962).
    [Crossref]
  21. T. Amano, P. F. Bernath, and A. R. W. McKellar, “Direct observation of the ν1 and ν3 fundamental bands of NH2 by difference frequency laser spectroscopy,” J. Mol. Spectrosc. 94, 100–113 (1982).
    [Crossref]

1985 (1)

1984 (2)

H. Adams, D. Reinert, P. Kalkert, and W. Urban, “A differential detection scheme for Faraday rotation spectroscopy with a color center laser,” Appl. Phys. B 34, 179–185 (1984).
[Crossref]

H. Adams, J. L. Hall, R. F. Curl, J. V. V. Kasper, and F. K. Tittel, “Sensitivity improvement of tone-burst modulated spectroscopy with a color-center laser,” J. Opt. Soc Am. B 1, 710–714 (1984).
[Crossref]

1983 (3)

C. S. Gudeman, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Velocity-modulated infrared spectroscopy of molecular ions: the ν1 band of HCO+,” Phys. Rev. Lett. 50, 727–731 (1983).
[Crossref]

H. Petek, D. J. Nesbitt, P. R. Ogilby, and C. B. Moore, “Infrared flash kinetic spectroscopy: the ν1 and ν3 spectra of singlet methylene,” J. Phys. Chem. 87, 5367–5371 (1983).
[Crossref]

C. S. Gudemann, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Tone-burst modulated color center laser spectroscopy,” Opt. Lett. 8, 310–315 (1983).
[Crossref]

1982 (3)

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Computer control of broadly tunable lasers: conversion of a color center laser into a high resolution spectrometer,” Appl. Opt. 21, 236–247 (1982).
[Crossref] [PubMed]

G. A. Laguna and S. L. Baughcum, “Real-time detection of methyl radicals by diode laser absorption at 608 cm−1,” Chem. Phys. Lett. 88, 568–571 (1982).
[Crossref]

T. Amano, P. F. Bernath, and A. R. W. McKellar, “Direct observation of the ν1 and ν3 fundamental bands of NH2 by difference frequency laser spectroscopy,” J. Mol. Spectrosc. 94, 100–113 (1982).
[Crossref]

1981 (3)

D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
[Crossref]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Observation of the 2P1/2 ← 2P3/2 transition of the Br atom by color center laser spectroscopy,” Chem. Phys. Lett. 77, 211–213 (1981).
[Crossref]

F. Magnotta, D. J. Nesbitt, and S. R. Leone, “Excimer laser flash photolysis studies of translational to vibrational energy transfer,” Chem. Phys. Lett. 83, 21–25 (1981).
[Crossref]

1980 (2)

G. Litfin, R. F. Curl, C. R. Pollock, and F. K. Tittel, “Sensitivity enhancement of laser absorption spectroscopy by magnetic rotation effect,” J. Chem. Phys. 72, 6602–6605 (1980).
[Crossref]

K. C. Kim, M. J. Reisfeld, and W. B. Person, “Diode laser spectroscopy of the transient UF5 radical following laser photolysis of UF6,” J. Mol. Struct. 60, 205–213 (1980).
[Crossref]

1976 (1)

J. P. Maillard, J. Chauville, and A. W. Mantz, “High-resolution emission spectrum of OH in an oxyacetylene flame from 3.7 to 0.9 μm,” J. Mol. Spectrosc. 63, 120–141 (1976).
[Crossref]

1973 (1)

E. Luc-Koenig, C. Morrillon, and J. Verges, “Etude de la transition interdite 2P1/2 ← 2P3/2 de la configuration np5 dans le brome et l’iode par spectrometrie de Fourier,” Physica 70, 175–189 (1973).
[Crossref]

1965 (1)

1964 (1)

This data processing often included Savitzky–Golay numerical smoothing methods.A. Savitzky and M. J. E. Golay, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 36, 1627–1639 (1964);J. Steinier, Y. Ter-monia, and J. Deltour, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 44, 1906–1909 (1972).
[Crossref] [PubMed]

1962 (1)

J. R. McNesby, I. Tanaka, and H. Okabe, “Vacuum ultraviolet photochemistry. III. Primary processes in the vacuum ultraviolet photolysis of water and ammonia,” J. Chem. Phys. 36, 605–607 (1962).
[Crossref]

Adams, H.

J. Hall, H. Adams, J. V. V. Kasper, R. F. Curl, and F. K. Tittel, J. Opt. Soc. Am. B 2, 781–785 (1985).
[Crossref]

H. Adams, D. Reinert, P. Kalkert, and W. Urban, “A differential detection scheme for Faraday rotation spectroscopy with a color center laser,” Appl. Phys. B 34, 179–185 (1984).
[Crossref]

H. Adams, J. L. Hall, R. F. Curl, J. V. V. Kasper, and F. K. Tittel, “Sensitivity improvement of tone-burst modulated spectroscopy with a color-center laser,” J. Opt. Soc Am. B 1, 710–714 (1984).
[Crossref]

J. Hall, H. Adams, L. A. Russell, J. V. V. Kasper, F. K. Tittel, and R. F. Curl, “Kinetic spectroscopy with the color center laser,” in Proceedings of the International Conference on Lasers’83, R. C. Powell, ed. (STS, McLean, Va., 1985).

Amano, T.

T. Amano, P. F. Bernath, and A. R. W. McKellar, “Direct observation of the ν1 and ν3 fundamental bands of NH2 by difference frequency laser spectroscopy,” J. Mol. Spectrosc. 94, 100–113 (1982).
[Crossref]

Avouris, Ph.

D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
[Crossref]

Baughcum, S. L.

G. A. Laguna and S. L. Baughcum, “Real-time detection of methyl radicals by diode laser absorption at 608 cm−1,” Chem. Phys. Lett. 88, 568–571 (1982).
[Crossref]

Begemann, M. H.

C. S. Gudeman, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Velocity-modulated infrared spectroscopy of molecular ions: the ν1 band of HCO+,” Phys. Rev. Lett. 50, 727–731 (1983).
[Crossref]

C. S. Gudemann, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Tone-burst modulated color center laser spectroscopy,” Opt. Lett. 8, 310–315 (1983).
[Crossref]

Bernath, P. F.

T. Amano, P. F. Bernath, and A. R. W. McKellar, “Direct observation of the ν1 and ν3 fundamental bands of NH2 by difference frequency laser spectroscopy,” J. Mol. Spectrosc. 94, 100–113 (1982).
[Crossref]

Bethune, D. S.

D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
[Crossref]

Chauville, J.

J. P. Maillard, J. Chauville, and A. W. Mantz, “High-resolution emission spectrum of OH in an oxyacetylene flame from 3.7 to 0.9 μm,” J. Mol. Spectrosc. 63, 120–141 (1976).
[Crossref]

Curl, R. F.

J. Hall, H. Adams, J. V. V. Kasper, R. F. Curl, and F. K. Tittel, J. Opt. Soc. Am. B 2, 781–785 (1985).
[Crossref]

H. Adams, J. L. Hall, R. F. Curl, J. V. V. Kasper, and F. K. Tittel, “Sensitivity improvement of tone-burst modulated spectroscopy with a color-center laser,” J. Opt. Soc Am. B 1, 710–714 (1984).
[Crossref]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Computer control of broadly tunable lasers: conversion of a color center laser into a high resolution spectrometer,” Appl. Opt. 21, 236–247 (1982).
[Crossref] [PubMed]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Observation of the 2P1/2 ← 2P3/2 transition of the Br atom by color center laser spectroscopy,” Chem. Phys. Lett. 77, 211–213 (1981).
[Crossref]

G. Litfin, R. F. Curl, C. R. Pollock, and F. K. Tittel, “Sensitivity enhancement of laser absorption spectroscopy by magnetic rotation effect,” J. Chem. Phys. 72, 6602–6605 (1980).
[Crossref]

J. Hall, H. Adams, L. A. Russell, J. V. V. Kasper, F. K. Tittel, and R. F. Curl, “Kinetic spectroscopy with the color center laser,” in Proceedings of the International Conference on Lasers’83, R. C. Powell, ed. (STS, McLean, Va., 1985).

Golay, M. J. E.

This data processing often included Savitzky–Golay numerical smoothing methods.A. Savitzky and M. J. E. Golay, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 36, 1627–1639 (1964);J. Steinier, Y. Ter-monia, and J. Deltour, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 44, 1906–1909 (1972).
[Crossref] [PubMed]

Gudeman, C. S.

C. S. Gudeman, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Velocity-modulated infrared spectroscopy of molecular ions: the ν1 band of HCO+,” Phys. Rev. Lett. 50, 727–731 (1983).
[Crossref]

Gudemann, C. S.

Hall, J.

J. Hall, H. Adams, J. V. V. Kasper, R. F. Curl, and F. K. Tittel, J. Opt. Soc. Am. B 2, 781–785 (1985).
[Crossref]

J. Hall, H. Adams, L. A. Russell, J. V. V. Kasper, F. K. Tittel, and R. F. Curl, “Kinetic spectroscopy with the color center laser,” in Proceedings of the International Conference on Lasers’83, R. C. Powell, ed. (STS, McLean, Va., 1985).

Hall, J. L.

H. Adams, J. L. Hall, R. F. Curl, J. V. V. Kasper, and F. K. Tittel, “Sensitivity improvement of tone-burst modulated spectroscopy with a color-center laser,” J. Opt. Soc Am. B 1, 710–714 (1984).
[Crossref]

Herr, K. C.

Hinkley, E. D.

E. D. Hinkley, R. T. Ku, and P. L. Kelley, in Laser Monitoring of the Atmosphere, E. D. Hinkley, ed. (Springer-Verlag, Berlin, 1976), Chap.6, p. 244.

Kalkert, P.

H. Adams, D. Reinert, P. Kalkert, and W. Urban, “A differential detection scheme for Faraday rotation spectroscopy with a color center laser,” Appl. Phys. B 34, 179–185 (1984).
[Crossref]

Kasper, J. V. V.

J. Hall, H. Adams, J. V. V. Kasper, R. F. Curl, and F. K. Tittel, J. Opt. Soc. Am. B 2, 781–785 (1985).
[Crossref]

H. Adams, J. L. Hall, R. F. Curl, J. V. V. Kasper, and F. K. Tittel, “Sensitivity improvement of tone-burst modulated spectroscopy with a color-center laser,” J. Opt. Soc Am. B 1, 710–714 (1984).
[Crossref]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Computer control of broadly tunable lasers: conversion of a color center laser into a high resolution spectrometer,” Appl. Opt. 21, 236–247 (1982).
[Crossref] [PubMed]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Observation of the 2P1/2 ← 2P3/2 transition of the Br atom by color center laser spectroscopy,” Chem. Phys. Lett. 77, 211–213 (1981).
[Crossref]

J. Hall, H. Adams, L. A. Russell, J. V. V. Kasper, F. K. Tittel, and R. F. Curl, “Kinetic spectroscopy with the color center laser,” in Proceedings of the International Conference on Lasers’83, R. C. Powell, ed. (STS, McLean, Va., 1985).

Kelley, P. L.

E. D. Hinkley, R. T. Ku, and P. L. Kelley, in Laser Monitoring of the Atmosphere, E. D. Hinkley, ed. (Springer-Verlag, Berlin, 1976), Chap.6, p. 244.

Kim, K. C.

K. C. Kim, M. J. Reisfeld, and W. B. Person, “Diode laser spectroscopy of the transient UF5 radical following laser photolysis of UF6,” J. Mol. Struct. 60, 205–213 (1980).
[Crossref]

Ku, R. T.

E. D. Hinkley, R. T. Ku, and P. L. Kelley, in Laser Monitoring of the Atmosphere, E. D. Hinkley, ed. (Springer-Verlag, Berlin, 1976), Chap.6, p. 244.

Laguna, G. A.

G. A. Laguna and S. L. Baughcum, “Real-time detection of methyl radicals by diode laser absorption at 608 cm−1,” Chem. Phys. Lett. 88, 568–571 (1982).
[Crossref]

Lankard, J. R.

D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
[Crossref]

Leone, S. R.

F. Magnotta, D. J. Nesbitt, and S. R. Leone, “Excimer laser flash photolysis studies of translational to vibrational energy transfer,” Chem. Phys. Lett. 83, 21–25 (1981).
[Crossref]

Litfin, G.

G. Litfin, R. F. Curl, C. R. Pollock, and F. K. Tittel, “Sensitivity enhancement of laser absorption spectroscopy by magnetic rotation effect,” J. Chem. Phys. 72, 6602–6605 (1980).
[Crossref]

Luc-Koenig, E.

E. Luc-Koenig, C. Morrillon, and J. Verges, “Etude de la transition interdite 2P1/2 ← 2P3/2 de la configuration np5 dans le brome et l’iode par spectrometrie de Fourier,” Physica 70, 175–189 (1973).
[Crossref]

Magnotta, F.

F. Magnotta, D. J. Nesbitt, and S. R. Leone, “Excimer laser flash photolysis studies of translational to vibrational energy transfer,” Chem. Phys. Lett. 83, 21–25 (1981).
[Crossref]

Maillard, J. P.

J. P. Maillard, J. Chauville, and A. W. Mantz, “High-resolution emission spectrum of OH in an oxyacetylene flame from 3.7 to 0.9 μm,” J. Mol. Spectrosc. 63, 120–141 (1976).
[Crossref]

Mantz, A. W.

J. P. Maillard, J. Chauville, and A. W. Mantz, “High-resolution emission spectrum of OH in an oxyacetylene flame from 3.7 to 0.9 μm,” J. Mol. Spectrosc. 63, 120–141 (1976).
[Crossref]

McKellar, A. R. W.

T. Amano, P. F. Bernath, and A. R. W. McKellar, “Direct observation of the ν1 and ν3 fundamental bands of NH2 by difference frequency laser spectroscopy,” J. Mol. Spectrosc. 94, 100–113 (1982).
[Crossref]

McNesby, J. R.

J. R. McNesby, I. Tanaka, and H. Okabe, “Vacuum ultraviolet photochemistry. III. Primary processes in the vacuum ultraviolet photolysis of water and ammonia,” J. Chem. Phys. 36, 605–607 (1962).
[Crossref]

Moore, C. B.

H. Petek, D. J. Nesbitt, P. R. Ogilby, and C. B. Moore, “Infrared flash kinetic spectroscopy: the ν1 and ν3 spectra of singlet methylene,” J. Phys. Chem. 87, 5367–5371 (1983).
[Crossref]

Morrillon, C.

E. Luc-Koenig, C. Morrillon, and J. Verges, “Etude de la transition interdite 2P1/2 ← 2P3/2 de la configuration np5 dans le brome et l’iode par spectrometrie de Fourier,” Physica 70, 175–189 (1973).
[Crossref]

Nesbitt, D. J.

H. Petek, D. J. Nesbitt, P. R. Ogilby, and C. B. Moore, “Infrared flash kinetic spectroscopy: the ν1 and ν3 spectra of singlet methylene,” J. Phys. Chem. 87, 5367–5371 (1983).
[Crossref]

F. Magnotta, D. J. Nesbitt, and S. R. Leone, “Excimer laser flash photolysis studies of translational to vibrational energy transfer,” Chem. Phys. Lett. 83, 21–25 (1981).
[Crossref]

Ogilby, P. R.

H. Petek, D. J. Nesbitt, P. R. Ogilby, and C. B. Moore, “Infrared flash kinetic spectroscopy: the ν1 and ν3 spectra of singlet methylene,” J. Phys. Chem. 87, 5367–5371 (1983).
[Crossref]

Okabe, H.

J. R. McNesby, I. Tanaka, and H. Okabe, “Vacuum ultraviolet photochemistry. III. Primary processes in the vacuum ultraviolet photolysis of water and ammonia,” J. Chem. Phys. 36, 605–607 (1962).
[Crossref]

Person, W. B.

K. C. Kim, M. J. Reisfeld, and W. B. Person, “Diode laser spectroscopy of the transient UF5 radical following laser photolysis of UF6,” J. Mol. Struct. 60, 205–213 (1980).
[Crossref]

Petek, H.

H. Petek, D. J. Nesbitt, P. R. Ogilby, and C. B. Moore, “Infrared flash kinetic spectroscopy: the ν1 and ν3 spectra of singlet methylene,” J. Phys. Chem. 87, 5367–5371 (1983).
[Crossref]

Pfaff, J.

C. S. Gudeman, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Velocity-modulated infrared spectroscopy of molecular ions: the ν1 band of HCO+,” Phys. Rev. Lett. 50, 727–731 (1983).
[Crossref]

C. S. Gudemann, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Tone-burst modulated color center laser spectroscopy,” Opt. Lett. 8, 310–315 (1983).
[Crossref]

Pimentel, G. C.

Plecenik, R. M.

D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
[Crossref]

Pollock, C. R.

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Computer control of broadly tunable lasers: conversion of a color center laser into a high resolution spectrometer,” Appl. Opt. 21, 236–247 (1982).
[Crossref] [PubMed]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Observation of the 2P1/2 ← 2P3/2 transition of the Br atom by color center laser spectroscopy,” Chem. Phys. Lett. 77, 211–213 (1981).
[Crossref]

G. Litfin, R. F. Curl, C. R. Pollock, and F. K. Tittel, “Sensitivity enhancement of laser absorption spectroscopy by magnetic rotation effect,” J. Chem. Phys. 72, 6602–6605 (1980).
[Crossref]

Reinert, D.

H. Adams, D. Reinert, P. Kalkert, and W. Urban, “A differential detection scheme for Faraday rotation spectroscopy with a color center laser,” Appl. Phys. B 34, 179–185 (1984).
[Crossref]

Reisfeld, M. J.

K. C. Kim, M. J. Reisfeld, and W. B. Person, “Diode laser spectroscopy of the transient UF5 radical following laser photolysis of UF6,” J. Mol. Struct. 60, 205–213 (1980).
[Crossref]

Russell, L. A.

J. Hall, H. Adams, L. A. Russell, J. V. V. Kasper, F. K. Tittel, and R. F. Curl, “Kinetic spectroscopy with the color center laser,” in Proceedings of the International Conference on Lasers’83, R. C. Powell, ed. (STS, McLean, Va., 1985).

Savitzky, A.

This data processing often included Savitzky–Golay numerical smoothing methods.A. Savitzky and M. J. E. Golay, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 36, 1627–1639 (1964);J. Steinier, Y. Ter-monia, and J. Deltour, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 44, 1906–1909 (1972).
[Crossref] [PubMed]

Saykally, R. J.

C. S. Gudeman, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Velocity-modulated infrared spectroscopy of molecular ions: the ν1 band of HCO+,” Phys. Rev. Lett. 50, 727–731 (1983).
[Crossref]

C. S. Gudemann, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Tone-burst modulated color center laser spectroscopy,” Opt. Lett. 8, 310–315 (1983).
[Crossref]

Schell-Sorokin, A. J.

D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
[Crossref]

Sorokin, P. P.

D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
[Crossref]

Tanaka, I.

J. R. McNesby, I. Tanaka, and H. Okabe, “Vacuum ultraviolet photochemistry. III. Primary processes in the vacuum ultraviolet photolysis of water and ammonia,” J. Chem. Phys. 36, 605–607 (1962).
[Crossref]

Tittel, F. K.

J. Hall, H. Adams, J. V. V. Kasper, R. F. Curl, and F. K. Tittel, J. Opt. Soc. Am. B 2, 781–785 (1985).
[Crossref]

H. Adams, J. L. Hall, R. F. Curl, J. V. V. Kasper, and F. K. Tittel, “Sensitivity improvement of tone-burst modulated spectroscopy with a color-center laser,” J. Opt. Soc Am. B 1, 710–714 (1984).
[Crossref]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Computer control of broadly tunable lasers: conversion of a color center laser into a high resolution spectrometer,” Appl. Opt. 21, 236–247 (1982).
[Crossref] [PubMed]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Observation of the 2P1/2 ← 2P3/2 transition of the Br atom by color center laser spectroscopy,” Chem. Phys. Lett. 77, 211–213 (1981).
[Crossref]

G. Litfin, R. F. Curl, C. R. Pollock, and F. K. Tittel, “Sensitivity enhancement of laser absorption spectroscopy by magnetic rotation effect,” J. Chem. Phys. 72, 6602–6605 (1980).
[Crossref]

J. Hall, H. Adams, L. A. Russell, J. V. V. Kasper, F. K. Tittel, and R. F. Curl, “Kinetic spectroscopy with the color center laser,” in Proceedings of the International Conference on Lasers’83, R. C. Powell, ed. (STS, McLean, Va., 1985).

Urban, W.

H. Adams, D. Reinert, P. Kalkert, and W. Urban, “A differential detection scheme for Faraday rotation spectroscopy with a color center laser,” Appl. Phys. B 34, 179–185 (1984).
[Crossref]

Verges, J.

E. Luc-Koenig, C. Morrillon, and J. Verges, “Etude de la transition interdite 2P1/2 ← 2P3/2 de la configuration np5 dans le brome et l’iode par spectrometrie de Fourier,” Physica 70, 175–189 (1973).
[Crossref]

Anal. Chem. (1)

This data processing often included Savitzky–Golay numerical smoothing methods.A. Savitzky and M. J. E. Golay, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 36, 1627–1639 (1964);J. Steinier, Y. Ter-monia, and J. Deltour, “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 44, 1906–1909 (1972).
[Crossref] [PubMed]

Appl. Opt. (2)

Appl. Phys. B (1)

H. Adams, D. Reinert, P. Kalkert, and W. Urban, “A differential detection scheme for Faraday rotation spectroscopy with a color center laser,” Appl. Phys. B 34, 179–185 (1984).
[Crossref]

Chem. Phys. Lett. (3)

G. A. Laguna and S. L. Baughcum, “Real-time detection of methyl radicals by diode laser absorption at 608 cm−1,” Chem. Phys. Lett. 88, 568–571 (1982).
[Crossref]

J. V. V. Kasper, C. R. Pollock, R. F. Curl, and F. K. Tittel, “Observation of the 2P1/2 ← 2P3/2 transition of the Br atom by color center laser spectroscopy,” Chem. Phys. Lett. 77, 211–213 (1981).
[Crossref]

F. Magnotta, D. J. Nesbitt, and S. R. Leone, “Excimer laser flash photolysis studies of translational to vibrational energy transfer,” Chem. Phys. Lett. 83, 21–25 (1981).
[Crossref]

J. Chem. Phys. (3)

G. Litfin, R. F. Curl, C. R. Pollock, and F. K. Tittel, “Sensitivity enhancement of laser absorption spectroscopy by magnetic rotation effect,” J. Chem. Phys. 72, 6602–6605 (1980).
[Crossref]

D. S. Bethune, J. R. Lankard, P. P. Sorokin, A. J. Schell-Sorokin, R. M. Plecenik, and Ph. Avouris, “Time-resolved infrared study of bimolecular reactions between tert-butyl radicals,” J. Chem. Phys. 75, 2231–2236 (1981).
[Crossref]

J. R. McNesby, I. Tanaka, and H. Okabe, “Vacuum ultraviolet photochemistry. III. Primary processes in the vacuum ultraviolet photolysis of water and ammonia,” J. Chem. Phys. 36, 605–607 (1962).
[Crossref]

J. Mol. Spectrosc. (2)

T. Amano, P. F. Bernath, and A. R. W. McKellar, “Direct observation of the ν1 and ν3 fundamental bands of NH2 by difference frequency laser spectroscopy,” J. Mol. Spectrosc. 94, 100–113 (1982).
[Crossref]

J. P. Maillard, J. Chauville, and A. W. Mantz, “High-resolution emission spectrum of OH in an oxyacetylene flame from 3.7 to 0.9 μm,” J. Mol. Spectrosc. 63, 120–141 (1976).
[Crossref]

J. Mol. Struct. (1)

K. C. Kim, M. J. Reisfeld, and W. B. Person, “Diode laser spectroscopy of the transient UF5 radical following laser photolysis of UF6,” J. Mol. Struct. 60, 205–213 (1980).
[Crossref]

J. Opt. Soc Am. B (1)

H. Adams, J. L. Hall, R. F. Curl, J. V. V. Kasper, and F. K. Tittel, “Sensitivity improvement of tone-burst modulated spectroscopy with a color-center laser,” J. Opt. Soc Am. B 1, 710–714 (1984).
[Crossref]

J. Opt. Soc. Am. B (1)

J. Phys. Chem. (1)

H. Petek, D. J. Nesbitt, P. R. Ogilby, and C. B. Moore, “Infrared flash kinetic spectroscopy: the ν1 and ν3 spectra of singlet methylene,” J. Phys. Chem. 87, 5367–5371 (1983).
[Crossref]

Opt. Lett. (1)

Phys. Rev. Lett. (1)

C. S. Gudeman, M. H. Begemann, J. Pfaff, and R. J. Saykally, “Velocity-modulated infrared spectroscopy of molecular ions: the ν1 band of HCO+,” Phys. Rev. Lett. 50, 727–731 (1983).
[Crossref]

Physica (1)

E. Luc-Koenig, C. Morrillon, and J. Verges, “Etude de la transition interdite 2P1/2 ← 2P3/2 de la configuration np5 dans le brome et l’iode par spectrometrie de Fourier,” Physica 70, 175–189 (1973).
[Crossref]

Other (2)

E. D. Hinkley, R. T. Ku, and P. L. Kelley, in Laser Monitoring of the Atmosphere, E. D. Hinkley, ed. (Springer-Verlag, Berlin, 1976), Chap.6, p. 244.

J. Hall, H. Adams, L. A. Russell, J. V. V. Kasper, F. K. Tittel, and R. F. Curl, “Kinetic spectroscopy with the color center laser,” in Proceedings of the International Conference on Lasers’83, R. C. Powell, ed. (STS, McLean, Va., 1985).

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Figures (8)

Fig. 1
Fig. 1

Experimental setup of several detection schemes. A specific scheme can be chosen by selecting the appropriate switch combination (S1, S2).

Fig. 2
Fig. 2

Bromine transient absorption of the strongest hyperfine component at 3685 cm−1 and comparison with a chopped beam trace (=100% absorption).

Fig. 3
Fig. 3

Normal absorption spectrum of the bromine-atom hyperfine structure at 3685 cm−1 obtained by taking at each frequency step the difference between the intensity measured at time t1 and t2 (see Fig. 2).

Fig. 4
Fig. 4

Normal absorption spectrum of the OH (1 ← 0)R(3.5)F1 transition using balanced detectors. The OH radical was produced by photolyzing a (N2O + H2O) mixture: N2O + → N2 + O(1D) followed by H2O + O(1D) → 2OH.

Fig. 5
Fig. 5

Transient absorption spectrum of photolyzed HNCO compared with the normal absorption spectrum. The HNCO sample contained impurities that also appear to be final photolysis products.

Fig. 6
Fig. 6

Magnetic-rotation spectrum of the bromine-atom fine structure using lock-in detection and the nearly crossed polarizer method (90° method). The dc magnetic field was about 300 G.

Fig. 7
Fig. 7

Magnetic-rotation spectrum of the OH (1 ← O) R(3.5) F1 (90° method).

Fig. 8
Fig. 8

(A) Transient absorption spectrum of NH2 produced by photolyzing NH3. (B) and (C) Comparison of the 45° with the 90° magnetic-rotation method. The 45° method allows almost total discrimination against precursor absorptions.

Equations (5)

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I TR = I 0 exp ( σ N L n ) ,
N = E / ( h ν exc A L ) .
I abs / I 0 = σ E n / ( h ν exc A ) ,
I abs / I 0 = 0.01 ,
NH 3 + h ν exc NH 2 + H .

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