Abstract

We report the spatially resolved detection of methyl radicals in a methane–air flat flame, using degenerate four-wave mixing (DFWM). A frequency-tripled dye laser pumped with a frequency-doubled Nd:YAG laser was used to access the Herzberg β1 band of methyl near 216 nm. Using a nearly phase-conjugate geometry, we detected methyl with high spatial resolution [0.2 mm (0.3 mm) vertical (horizontal) and ~6 mm longitudinal] and with good signal-to-noise ratio in a rich (ϕ = 1.55) flame. Compared with laser absorption spectra, DFWM spectra were much less influenced by a broad featureless background. From the absorption data, we measured the peak methyl concentration to be 650 parts in 106, resulting in an estimated DFWM detection limit of 65 parts in 106.

© 1995 Optical Society of America

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References

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  1. J. Warnatz, C. Chevalier, “Reactions in the C/H/C system,” in Combustion Chemistry, W. C. Gardiner, ed. (Springer-Verlag, New York, to be published).
  2. S. J. Harris, Appl. Phys. Lett. 23, 2298 (1990).
    [CrossRef]
  3. G. Herzberg, J. Shoosmith, Can. J. Phys. 34, 523 (1956).
    [CrossRef]
  4. D. F. Davidson, A. Y. Chang, M. D. Di Rosa, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 49, 559 (1993).
    [CrossRef]
  5. The reported value of kλ was later revised. SeeD. F. Davidson, M. D. Di Rosa, E. J. Chang, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 53, 581 (1995).
  6. T. Etzkorn, J. Fitzer, S. Muris, J. Wolfrum, Chem. Phys. Lett. 208, 307 (1993).
    [CrossRef]
  7. P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
    [CrossRef]
  8. K. C. Smyth, P. H. Taylor, Chem. Phys. Lett. 122, 518 (1985).
    [CrossRef]
  9. P. B. Kelly, S. G. Westre, Chem. Phys. Lett. 151, 253 (1988).
    [CrossRef]
  10. P. L. Holt, K. E. McCurdy, R. B. Weisman, J. S. Abrams, P. S. Engel, J. Chem. Phys. 81, 3349 (1984).
    [CrossRef]
  11. R. L. Farrow, D. J. Rakestraw, Science 257, 1894 (1992), and references therein.
    [CrossRef] [PubMed]
  12. R. L. Vander Wal, R. L. Farrow, D. J. Rakestraw, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1992), p. 1653.
    [CrossRef]
  13. M. N. Bui-Pham, J. A. Miller, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1994), p. 1309.
    [CrossRef]
  14. G. Herzberg, Molecular Spectra and Molecular Structure III. Electronic Spectra of Polyatomic Molecules (Van Nostrand Reinhold, New York, 1966).
  15. C. Yamada, E. Hirota, K. Kawaguchi, J. Chem. Phys. 75, 5256 (1981).
    [CrossRef]
  16. K. Glänzer, M. Quack, J. Troe, in Sixteenth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1977), p. 949.
    [CrossRef]
  17. A. B. Callear, M. P. Metcalfe, Chem. Phys. 14, 275 (1976).
    [CrossRef]
  18. V. Sick, M. Szabadi, “Einstein coefficients for oxygen B –X transitions used in laser-induced fluorescence experiments with tunable KrF excimer lasers,” J. Quant. Spectrosc. Radiat. Transfer (to be published).
  19. R. L. Abrams, J. F. Jam, R. C. Lind, D. G. Steel, in Optical Phase Conjugation, R. A. Fischer, ed. (Academic, New York, 1983).
  20. S. Williams, L. A. Rahn, P. H. Paul, J. W. Forsman, R. N. Zare, Opt. Lett. 19, 1681 (1994).
    [CrossRef] [PubMed]
  21. G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, Chem. Phys. Lett. 217, 112 (1994).
    [CrossRef]

1995 (2)

The reported value of kλ was later revised. SeeD. F. Davidson, M. D. Di Rosa, E. J. Chang, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 53, 581 (1995).

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

1994 (2)

S. Williams, L. A. Rahn, P. H. Paul, J. W. Forsman, R. N. Zare, Opt. Lett. 19, 1681 (1994).
[CrossRef] [PubMed]

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, Chem. Phys. Lett. 217, 112 (1994).
[CrossRef]

1993 (2)

D. F. Davidson, A. Y. Chang, M. D. Di Rosa, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 49, 559 (1993).
[CrossRef]

T. Etzkorn, J. Fitzer, S. Muris, J. Wolfrum, Chem. Phys. Lett. 208, 307 (1993).
[CrossRef]

1992 (1)

R. L. Farrow, D. J. Rakestraw, Science 257, 1894 (1992), and references therein.
[CrossRef] [PubMed]

1990 (1)

S. J. Harris, Appl. Phys. Lett. 23, 2298 (1990).
[CrossRef]

1988 (1)

P. B. Kelly, S. G. Westre, Chem. Phys. Lett. 151, 253 (1988).
[CrossRef]

1985 (1)

K. C. Smyth, P. H. Taylor, Chem. Phys. Lett. 122, 518 (1985).
[CrossRef]

1984 (1)

P. L. Holt, K. E. McCurdy, R. B. Weisman, J. S. Abrams, P. S. Engel, J. Chem. Phys. 81, 3349 (1984).
[CrossRef]

1981 (1)

C. Yamada, E. Hirota, K. Kawaguchi, J. Chem. Phys. 75, 5256 (1981).
[CrossRef]

1976 (1)

A. B. Callear, M. P. Metcalfe, Chem. Phys. 14, 275 (1976).
[CrossRef]

1956 (1)

G. Herzberg, J. Shoosmith, Can. J. Phys. 34, 523 (1956).
[CrossRef]

Abrams, J. S.

P. L. Holt, K. E. McCurdy, R. B. Weisman, J. S. Abrams, P. S. Engel, J. Chem. Phys. 81, 3349 (1984).
[CrossRef]

Abrams, R. L.

R. L. Abrams, J. F. Jam, R. C. Lind, D. G. Steel, in Optical Phase Conjugation, R. A. Fischer, ed. (Academic, New York, 1983).

Boogaarts, M. G. H.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, Chem. Phys. Lett. 217, 112 (1994).
[CrossRef]

Bui-Pham, M. N.

M. N. Bui-Pham, J. A. Miller, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1994), p. 1309.
[CrossRef]

Callear, A. B.

A. B. Callear, M. P. Metcalfe, Chem. Phys. 14, 275 (1976).
[CrossRef]

Chang, A. Y.

D. F. Davidson, A. Y. Chang, M. D. Di Rosa, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 49, 559 (1993).
[CrossRef]

Chang, E. J.

The reported value of kλ was later revised. SeeD. F. Davidson, M. D. Di Rosa, E. J. Chang, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 53, 581 (1995).

Chevalier, C.

J. Warnatz, C. Chevalier, “Reactions in the C/H/C system,” in Combustion Chemistry, W. C. Gardiner, ed. (Springer-Verlag, New York, to be published).

Dadamio, J. R.

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

Davidson, D. F.

The reported value of kλ was later revised. SeeD. F. Davidson, M. D. Di Rosa, E. J. Chang, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 53, 581 (1995).

D. F. Davidson, A. Y. Chang, M. D. Di Rosa, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 49, 559 (1993).
[CrossRef]

Di Rosa, M. D.

The reported value of kλ was later revised. SeeD. F. Davidson, M. D. Di Rosa, E. J. Chang, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 53, 581 (1995).

D. F. Davidson, A. Y. Chang, M. D. Di Rosa, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 49, 559 (1993).
[CrossRef]

Engel, P. S.

P. L. Holt, K. E. McCurdy, R. B. Weisman, J. S. Abrams, P. S. Engel, J. Chem. Phys. 81, 3349 (1984).
[CrossRef]

Etzkorn, T.

T. Etzkorn, J. Fitzer, S. Muris, J. Wolfrum, Chem. Phys. Lett. 208, 307 (1993).
[CrossRef]

Farrow, R. L.

R. L. Farrow, D. J. Rakestraw, Science 257, 1894 (1992), and references therein.
[CrossRef] [PubMed]

R. L. Vander Wal, R. L. Farrow, D. J. Rakestraw, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1992), p. 1653.
[CrossRef]

Fitzer, J.

T. Etzkorn, J. Fitzer, S. Muris, J. Wolfrum, Chem. Phys. Lett. 208, 307 (1993).
[CrossRef]

Forsman, J. W.

Glänzer, K.

K. Glänzer, M. Quack, J. Troe, in Sixteenth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1977), p. 949.
[CrossRef]

Hanson, R. K.

The reported value of kλ was later revised. SeeD. F. Davidson, M. D. Di Rosa, E. J. Chang, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 53, 581 (1995).

D. F. Davidson, A. Y. Chang, M. D. Di Rosa, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 49, 559 (1993).
[CrossRef]

Harris, S. J.

S. J. Harris, Appl. Phys. Lett. 23, 2298 (1990).
[CrossRef]

Herzberg, G.

G. Herzberg, J. Shoosmith, Can. J. Phys. 34, 523 (1956).
[CrossRef]

G. Herzberg, Molecular Spectra and Molecular Structure III. Electronic Spectra of Polyatomic Molecules (Van Nostrand Reinhold, New York, 1966).

Hirota, E.

C. Yamada, E. Hirota, K. Kawaguchi, J. Chem. Phys. 75, 5256 (1981).
[CrossRef]

Holt, P. L.

P. L. Holt, K. E. McCurdy, R. B. Weisman, J. S. Abrams, P. S. Engel, J. Chem. Phys. 81, 3349 (1984).
[CrossRef]

Jam, J. F.

R. L. Abrams, J. F. Jam, R. C. Lind, D. G. Steel, in Optical Phase Conjugation, R. A. Fischer, ed. (Academic, New York, 1983).

Jongma, R. T.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, Chem. Phys. Lett. 217, 112 (1994).
[CrossRef]

Kawaguchi, K.

C. Yamada, E. Hirota, K. Kawaguchi, J. Chem. Phys. 75, 5256 (1981).
[CrossRef]

Kelly, P. B.

P. B. Kelly, S. G. Westre, Chem. Phys. Lett. 151, 253 (1988).
[CrossRef]

Kruger, C. H.

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

Lind, R. C.

R. L. Abrams, J. F. Jam, R. C. Lind, D. G. Steel, in Optical Phase Conjugation, R. A. Fischer, ed. (Academic, New York, 1983).

Ma, Y.

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

McCurdy, K. E.

P. L. Holt, K. E. McCurdy, R. B. Weisman, J. S. Abrams, P. S. Engel, J. Chem. Phys. 81, 3349 (1984).
[CrossRef]

Meijer, G.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, Chem. Phys. Lett. 217, 112 (1994).
[CrossRef]

Metcalfe, M. P.

A. B. Callear, M. P. Metcalfe, Chem. Phys. 14, 275 (1976).
[CrossRef]

Miller, J. A.

M. N. Bui-Pham, J. A. Miller, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1994), p. 1309.
[CrossRef]

Muris, S.

T. Etzkorn, J. Fitzer, S. Muris, J. Wolfrum, Chem. Phys. Lett. 208, 307 (1993).
[CrossRef]

Owano, T. G.

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

Parker, D. H.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, Chem. Phys. Lett. 217, 112 (1994).
[CrossRef]

Paul, P. H.

Quack, M.

K. Glänzer, M. Quack, J. Troe, in Sixteenth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1977), p. 949.
[CrossRef]

Rahn, L. A.

Rakestraw, D. J.

R. L. Farrow, D. J. Rakestraw, Science 257, 1894 (1992), and references therein.
[CrossRef] [PubMed]

R. L. Vander Wal, R. L. Farrow, D. J. Rakestraw, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1992), p. 1653.
[CrossRef]

Shoosmith, J.

G. Herzberg, J. Shoosmith, Can. J. Phys. 34, 523 (1956).
[CrossRef]

Sick, V.

V. Sick, M. Szabadi, “Einstein coefficients for oxygen B –X transitions used in laser-induced fluorescence experiments with tunable KrF excimer lasers,” J. Quant. Spectrosc. Radiat. Transfer (to be published).

Smyth, K. C.

K. C. Smyth, P. H. Taylor, Chem. Phys. Lett. 122, 518 (1985).
[CrossRef]

Steel, D. G.

R. L. Abrams, J. F. Jam, R. C. Lind, D. G. Steel, in Optical Phase Conjugation, R. A. Fischer, ed. (Academic, New York, 1983).

Szabadi, M.

V. Sick, M. Szabadi, “Einstein coefficients for oxygen B –X transitions used in laser-induced fluorescence experiments with tunable KrF excimer lasers,” J. Quant. Spectrosc. Radiat. Transfer (to be published).

Taylor, P. H.

K. C. Smyth, P. H. Taylor, Chem. Phys. Lett. 122, 518 (1985).
[CrossRef]

Troe, J.

K. Glänzer, M. Quack, J. Troe, in Sixteenth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1977), p. 949.
[CrossRef]

Vander Wal, R. L.

R. L. Vander Wal, R. L. Farrow, D. J. Rakestraw, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1992), p. 1653.
[CrossRef]

Wahl, E. H.

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

Warnatz, J.

J. Warnatz, C. Chevalier, “Reactions in the C/H/C system,” in Combustion Chemistry, W. C. Gardiner, ed. (Springer-Verlag, New York, to be published).

Weisman, R. B.

P. L. Holt, K. E. McCurdy, R. B. Weisman, J. S. Abrams, P. S. Engel, J. Chem. Phys. 81, 3349 (1984).
[CrossRef]

Westre, S. G.

P. B. Kelly, S. G. Westre, Chem. Phys. Lett. 151, 253 (1988).
[CrossRef]

Williams, S.

Wodtke, A. M.

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, Chem. Phys. Lett. 217, 112 (1994).
[CrossRef]

Wolfrum, J.

T. Etzkorn, J. Fitzer, S. Muris, J. Wolfrum, Chem. Phys. Lett. 208, 307 (1993).
[CrossRef]

Yamada, C.

C. Yamada, E. Hirota, K. Kawaguchi, J. Chem. Phys. 75, 5256 (1981).
[CrossRef]

Zalicki, P.

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

Zare, R. N.

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

S. Williams, L. A. Rahn, P. H. Paul, J. W. Forsman, R. N. Zare, Opt. Lett. 19, 1681 (1994).
[CrossRef] [PubMed]

Appl. Phys. Lett. (1)

S. J. Harris, Appl. Phys. Lett. 23, 2298 (1990).
[CrossRef]

Can. J. Phys. (1)

G. Herzberg, J. Shoosmith, Can. J. Phys. 34, 523 (1956).
[CrossRef]

Chem. Phys. (1)

A. B. Callear, M. P. Metcalfe, Chem. Phys. 14, 275 (1976).
[CrossRef]

Chem. Phys. Lett. (5)

T. Etzkorn, J. Fitzer, S. Muris, J. Wolfrum, Chem. Phys. Lett. 208, 307 (1993).
[CrossRef]

P. Zalicki, Y. Ma, R. N. Zare, E. H. Wahl, J. R. Dadamio, T. G. Owano, C. H. Kruger, Chem. Phys. Lett. 234, 269 (1995).
[CrossRef]

K. C. Smyth, P. H. Taylor, Chem. Phys. Lett. 122, 518 (1985).
[CrossRef]

P. B. Kelly, S. G. Westre, Chem. Phys. Lett. 151, 253 (1988).
[CrossRef]

G. Meijer, M. G. H. Boogaarts, R. T. Jongma, D. H. Parker, A. M. Wodtke, Chem. Phys. Lett. 217, 112 (1994).
[CrossRef]

J. Chem. Phys. (2)

P. L. Holt, K. E. McCurdy, R. B. Weisman, J. S. Abrams, P. S. Engel, J. Chem. Phys. 81, 3349 (1984).
[CrossRef]

C. Yamada, E. Hirota, K. Kawaguchi, J. Chem. Phys. 75, 5256 (1981).
[CrossRef]

J. Quant. Spectrosc. Radiat. Transfer (2)

D. F. Davidson, A. Y. Chang, M. D. Di Rosa, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 49, 559 (1993).
[CrossRef]

The reported value of kλ was later revised. SeeD. F. Davidson, M. D. Di Rosa, E. J. Chang, R. K. Hanson, J. Quant. Spectrosc. Radiat. Transfer 53, 581 (1995).

Opt. Lett. (1)

Science (1)

R. L. Farrow, D. J. Rakestraw, Science 257, 1894 (1992), and references therein.
[CrossRef] [PubMed]

Other (7)

R. L. Vander Wal, R. L. Farrow, D. J. Rakestraw, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1992), p. 1653.
[CrossRef]

M. N. Bui-Pham, J. A. Miller, in Twenty-Fourth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1994), p. 1309.
[CrossRef]

G. Herzberg, Molecular Spectra and Molecular Structure III. Electronic Spectra of Polyatomic Molecules (Van Nostrand Reinhold, New York, 1966).

K. Glänzer, M. Quack, J. Troe, in Sixteenth Symposium (International) on Combustion (Combustion Institute, Pittsburgh, Pa., 1977), p. 949.
[CrossRef]

V. Sick, M. Szabadi, “Einstein coefficients for oxygen B –X transitions used in laser-induced fluorescence experiments with tunable KrF excimer lasers,” J. Quant. Spectrosc. Radiat. Transfer (to be published).

R. L. Abrams, J. F. Jam, R. C. Lind, D. G. Steel, in Optical Phase Conjugation, R. A. Fischer, ed. (Academic, New York, 1983).

J. Warnatz, C. Chevalier, “Reactions in the C/H/C system,” in Combustion Chemistry, W. C. Gardiner, ed. (Springer-Verlag, New York, to be published).

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Figures (2)

Fig. 1
Fig. 1

Single-pass absorption spectrum of CH3 measured 2.1 mm above the burner surface (top trace). A concentration of 650 parts in 106 CH3 radicals is calculated for this flame position. The dashed line indicates the broadband background absorption, dominating the overall absorption in this spectral range. This background has been added to the simulation of the spectrum (thick solid curve). The bottom trace shows a DFWM spectrum of CH3 measured with 200-μm beams at the same position. The two underlying broad features result from CH3, and the overlapping narrow peaks correspond to O2 Schumann–Runge transitions. Note that there is region at 46 185 cm−1 at the peak of the stronger CH3 band that is free of O2 interference.

Fig. 2
Fig. 2

Spatial CH3 profiles in a laminar methane–air flame at ϕ = 1.55. The measured profile (filled circles) was taken with 200-μm-diameter focused laser beams.

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