Abstract

A new time-resolved coherent Raman technique (three-color picosecond coherent anti-Stokes Raman scattering), which uses a backscattering geometry and three colors obtained from three different lasers, is demonstrated. The advantage of this technique over conventional two-color picosecond coherent anti-Stokes Raman scattering is that it is insensitive to sample morphology. It is used to study time-dependent vibrational dephasing from opaque, polycrystalline solids at low temperature. A quantitative treatment of the limiting apparatus time response, where each pulse has a different duration and where there is arrival-time jitter between the pulses, is derived. New measurements of vibrational dynamics in low-temperature carbon disulfide indicate that polycrystalline samples are more homogeneous, on a microscopic level, than the large single crystals used in previous work. Raman line broadening in a sample of naphthalene in which strain is induced intentionally by grinding and compression is also investigated.

© 1991 Optical Society of America

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References

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  1. L. Angeloni, R. Righini, P. R. Salvi, and V. Schettino, Chem. Phys. Lett. 154, 432 (1989).
    [Crossref]
  2. D. D. Dlott, in Laser Spectroscopy of Solids II, W. M. Yen, ed. (Springer-Verlag, Berlin, 1988), pp. 167–200.
  3. B. H. Hesp and D. A. Wiersma, Chem. Phys. Lett. 75, 423 (1980).
    [Crossref]
  4. P. L. Decola, R. M. Hochstrasser, and H. P. Trommsdorff, Chem. Phys. Lett. 72, 1 (1980).
    [Crossref]
  5. C. L. Schosser and D. D. Dlott, J. Chem. Phys. 80, 1394 (1984).
    [Crossref]
  6. E. L. Chronister and D. D. Dlott, J. Chem. Phys. 79, 5286 (1983); E. L. Chronister, J. R. Hill, and D. D. Dlott, J. Chim. Phys. Phys. Chim. Biol. 82, 159 (1985).
    [Crossref]
  7. J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
    [Crossref]
  8. J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
    [Crossref]
  9. P. Ranson, R. Ouillon, and S. Califano, Chem. Phys. 86, 115 (1984).
    [Crossref]
  10. S. Chen, X. Wen, and D. D. Dlott, “Low-temperature vibrational relaxation of high explosives” (submitted to J. Chem. Phys.
  11. A. C. Eckbreth, Appl. Phys. Lett. 32, 421 (1978).
    [Crossref]
  12. D. D. Dlott, C. L. Schosser, and E. L. Chronister, Chem. Phys. Lett. 90, 386 (1982).
    [Crossref]
  13. G. R. Fleming, Chemical Applications of Ultrafast Spectroscopy (Oxford, New York, 1986), p. 45.
  14. S. P. Velsko and R. M. Hochstrasser, J. Chim. Phys. Phys. Chim. Biol. 82, 153 (1985); J. Phys. Chem. 89, 2240 (1985).
  15. A. Laubereau and W. Kaiser, Rev. Mod. Phys. 50, 608 (1978).
    [Crossref]
  16. D. D. Dlott, Annu. Rev. Phys. Chem. 37, 157 (1986).
    [Crossref]
  17. M. L. Geirnaert, G. M. Gale, and C. Flytzanis, Phys. Rev. Lett. 52, 815 (1984).
    [Crossref]
  18. W. Zinth, M. C. Nuss, and W. Kaiser, Chem. Phys. Lett. 88, 257 (1982).
    [Crossref]
  19. C. B. Harris, H. Auweter, and S. M. George, Phys. Rev. Lett. 44, 737 (1980); S. M. George, H. Auweter, and C. B. Harris, J. Chem. Phys. 73, 5573 (1980).
    [Crossref]
  20. A. Bree and R. A. Kydd, Spectrochim. Acta Part A 26, 1791 (1970).
    [Crossref]
  21. M. Nicol, M. Vernon, and J. T. Woo, J. Chem. Phys. 63, 1992 (1975).
    [Crossref]

1989 (1)

L. Angeloni, R. Righini, P. R. Salvi, and V. Schettino, Chem. Phys. Lett. 154, 432 (1989).
[Crossref]

1988 (2)

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
[Crossref]

1986 (1)

D. D. Dlott, Annu. Rev. Phys. Chem. 37, 157 (1986).
[Crossref]

1985 (1)

S. P. Velsko and R. M. Hochstrasser, J. Chim. Phys. Phys. Chim. Biol. 82, 153 (1985); J. Phys. Chem. 89, 2240 (1985).

1984 (3)

M. L. Geirnaert, G. M. Gale, and C. Flytzanis, Phys. Rev. Lett. 52, 815 (1984).
[Crossref]

P. Ranson, R. Ouillon, and S. Califano, Chem. Phys. 86, 115 (1984).
[Crossref]

C. L. Schosser and D. D. Dlott, J. Chem. Phys. 80, 1394 (1984).
[Crossref]

1983 (1)

E. L. Chronister and D. D. Dlott, J. Chem. Phys. 79, 5286 (1983); E. L. Chronister, J. R. Hill, and D. D. Dlott, J. Chim. Phys. Phys. Chim. Biol. 82, 159 (1985).
[Crossref]

1982 (2)

W. Zinth, M. C. Nuss, and W. Kaiser, Chem. Phys. Lett. 88, 257 (1982).
[Crossref]

D. D. Dlott, C. L. Schosser, and E. L. Chronister, Chem. Phys. Lett. 90, 386 (1982).
[Crossref]

1980 (3)

C. B. Harris, H. Auweter, and S. M. George, Phys. Rev. Lett. 44, 737 (1980); S. M. George, H. Auweter, and C. B. Harris, J. Chem. Phys. 73, 5573 (1980).
[Crossref]

B. H. Hesp and D. A. Wiersma, Chem. Phys. Lett. 75, 423 (1980).
[Crossref]

P. L. Decola, R. M. Hochstrasser, and H. P. Trommsdorff, Chem. Phys. Lett. 72, 1 (1980).
[Crossref]

1978 (2)

A. C. Eckbreth, Appl. Phys. Lett. 32, 421 (1978).
[Crossref]

A. Laubereau and W. Kaiser, Rev. Mod. Phys. 50, 608 (1978).
[Crossref]

1975 (1)

M. Nicol, M. Vernon, and J. T. Woo, J. Chem. Phys. 63, 1992 (1975).
[Crossref]

1970 (1)

A. Bree and R. A. Kydd, Spectrochim. Acta Part A 26, 1791 (1970).
[Crossref]

Angeloni, L.

L. Angeloni, R. Righini, P. R. Salvi, and V. Schettino, Chem. Phys. Lett. 154, 432 (1989).
[Crossref]

Auweter, H.

C. B. Harris, H. Auweter, and S. M. George, Phys. Rev. Lett. 44, 737 (1980); S. M. George, H. Auweter, and C. B. Harris, J. Chem. Phys. 73, 5573 (1980).
[Crossref]

Bree, A.

A. Bree and R. A. Kydd, Spectrochim. Acta Part A 26, 1791 (1970).
[Crossref]

Califano, S.

P. Ranson, R. Ouillon, and S. Califano, Chem. Phys. 86, 115 (1984).
[Crossref]

Chang, T. -C.

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
[Crossref]

Chen, S.

S. Chen, X. Wen, and D. D. Dlott, “Low-temperature vibrational relaxation of high explosives” (submitted to J. Chem. Phys.

Chronister, E. L.

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
[Crossref]

E. L. Chronister and D. D. Dlott, J. Chem. Phys. 79, 5286 (1983); E. L. Chronister, J. R. Hill, and D. D. Dlott, J. Chim. Phys. Phys. Chim. Biol. 82, 159 (1985).
[Crossref]

D. D. Dlott, C. L. Schosser, and E. L. Chronister, Chem. Phys. Lett. 90, 386 (1982).
[Crossref]

Decola, P. L.

P. L. Decola, R. M. Hochstrasser, and H. P. Trommsdorff, Chem. Phys. Lett. 72, 1 (1980).
[Crossref]

Dlott, D. D.

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
[Crossref]

D. D. Dlott, Annu. Rev. Phys. Chem. 37, 157 (1986).
[Crossref]

C. L. Schosser and D. D. Dlott, J. Chem. Phys. 80, 1394 (1984).
[Crossref]

E. L. Chronister and D. D. Dlott, J. Chem. Phys. 79, 5286 (1983); E. L. Chronister, J. R. Hill, and D. D. Dlott, J. Chim. Phys. Phys. Chim. Biol. 82, 159 (1985).
[Crossref]

D. D. Dlott, C. L. Schosser, and E. L. Chronister, Chem. Phys. Lett. 90, 386 (1982).
[Crossref]

S. Chen, X. Wen, and D. D. Dlott, “Low-temperature vibrational relaxation of high explosives” (submitted to J. Chem. Phys.

D. D. Dlott, in Laser Spectroscopy of Solids II, W. M. Yen, ed. (Springer-Verlag, Berlin, 1988), pp. 167–200.

Eckbreth, A. C.

A. C. Eckbreth, Appl. Phys. Lett. 32, 421 (1978).
[Crossref]

Fleming, G. R.

G. R. Fleming, Chemical Applications of Ultrafast Spectroscopy (Oxford, New York, 1986), p. 45.

Flytzanis, C.

M. L. Geirnaert, G. M. Gale, and C. Flytzanis, Phys. Rev. Lett. 52, 815 (1984).
[Crossref]

Gale, G. M.

M. L. Geirnaert, G. M. Gale, and C. Flytzanis, Phys. Rev. Lett. 52, 815 (1984).
[Crossref]

Geirnaert, M. L.

M. L. Geirnaert, G. M. Gale, and C. Flytzanis, Phys. Rev. Lett. 52, 815 (1984).
[Crossref]

George, S. M.

C. B. Harris, H. Auweter, and S. M. George, Phys. Rev. Lett. 44, 737 (1980); S. M. George, H. Auweter, and C. B. Harris, J. Chem. Phys. 73, 5573 (1980).
[Crossref]

Harris, C. B.

C. B. Harris, H. Auweter, and S. M. George, Phys. Rev. Lett. 44, 737 (1980); S. M. George, H. Auweter, and C. B. Harris, J. Chem. Phys. 73, 5573 (1980).
[Crossref]

Hesp, B. H.

B. H. Hesp and D. A. Wiersma, Chem. Phys. Lett. 75, 423 (1980).
[Crossref]

Hill, J. R.

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
[Crossref]

Hochstrasser, R. M.

S. P. Velsko and R. M. Hochstrasser, J. Chim. Phys. Phys. Chim. Biol. 82, 153 (1985); J. Phys. Chem. 89, 2240 (1985).

P. L. Decola, R. M. Hochstrasser, and H. P. Trommsdorff, Chem. Phys. Lett. 72, 1 (1980).
[Crossref]

Kaiser, W.

W. Zinth, M. C. Nuss, and W. Kaiser, Chem. Phys. Lett. 88, 257 (1982).
[Crossref]

A. Laubereau and W. Kaiser, Rev. Mod. Phys. 50, 608 (1978).
[Crossref]

Kim, H.

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
[Crossref]

Kydd, R. A.

A. Bree and R. A. Kydd, Spectrochim. Acta Part A 26, 1791 (1970).
[Crossref]

Laubereau, A.

A. Laubereau and W. Kaiser, Rev. Mod. Phys. 50, 608 (1978).
[Crossref]

Nicol, M.

M. Nicol, M. Vernon, and J. T. Woo, J. Chem. Phys. 63, 1992 (1975).
[Crossref]

Nuss, M. C.

W. Zinth, M. C. Nuss, and W. Kaiser, Chem. Phys. Lett. 88, 257 (1982).
[Crossref]

Ouillon, R.

P. Ranson, R. Ouillon, and S. Califano, Chem. Phys. 86, 115 (1984).
[Crossref]

Postlewaite, J. C.

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
[Crossref]

Ranson, P.

P. Ranson, R. Ouillon, and S. Califano, Chem. Phys. 86, 115 (1984).
[Crossref]

Righini, R.

L. Angeloni, R. Righini, P. R. Salvi, and V. Schettino, Chem. Phys. Lett. 154, 432 (1989).
[Crossref]

Salvi, P. R.

L. Angeloni, R. Righini, P. R. Salvi, and V. Schettino, Chem. Phys. Lett. 154, 432 (1989).
[Crossref]

Schettino, V.

L. Angeloni, R. Righini, P. R. Salvi, and V. Schettino, Chem. Phys. Lett. 154, 432 (1989).
[Crossref]

Schosser, C. L.

C. L. Schosser and D. D. Dlott, J. Chem. Phys. 80, 1394 (1984).
[Crossref]

D. D. Dlott, C. L. Schosser, and E. L. Chronister, Chem. Phys. Lett. 90, 386 (1982).
[Crossref]

Trommsdorff, H. P.

P. L. Decola, R. M. Hochstrasser, and H. P. Trommsdorff, Chem. Phys. Lett. 72, 1 (1980).
[Crossref]

Velsko, S. P.

S. P. Velsko and R. M. Hochstrasser, J. Chim. Phys. Phys. Chim. Biol. 82, 153 (1985); J. Phys. Chem. 89, 2240 (1985).

Vernon, M.

M. Nicol, M. Vernon, and J. T. Woo, J. Chem. Phys. 63, 1992 (1975).
[Crossref]

Wen, X.

S. Chen, X. Wen, and D. D. Dlott, “Low-temperature vibrational relaxation of high explosives” (submitted to J. Chem. Phys.

Wiersma, D. A.

B. H. Hesp and D. A. Wiersma, Chem. Phys. Lett. 75, 423 (1980).
[Crossref]

Woo, J. T.

M. Nicol, M. Vernon, and J. T. Woo, J. Chem. Phys. 63, 1992 (1975).
[Crossref]

Zinth, W.

W. Zinth, M. C. Nuss, and W. Kaiser, Chem. Phys. Lett. 88, 257 (1982).
[Crossref]

Annu. Rev. Phys. Chem. (1)

D. D. Dlott, Annu. Rev. Phys. Chem. 37, 157 (1986).
[Crossref]

Appl. Phys. Lett. (1)

A. C. Eckbreth, Appl. Phys. Lett. 32, 421 (1978).
[Crossref]

Chem. Phys. (1)

P. Ranson, R. Ouillon, and S. Califano, Chem. Phys. 86, 115 (1984).
[Crossref]

Chem. Phys. Lett. (5)

L. Angeloni, R. Righini, P. R. Salvi, and V. Schettino, Chem. Phys. Lett. 154, 432 (1989).
[Crossref]

B. H. Hesp and D. A. Wiersma, Chem. Phys. Lett. 75, 423 (1980).
[Crossref]

P. L. Decola, R. M. Hochstrasser, and H. P. Trommsdorff, Chem. Phys. Lett. 72, 1 (1980).
[Crossref]

D. D. Dlott, C. L. Schosser, and E. L. Chronister, Chem. Phys. Lett. 90, 386 (1982).
[Crossref]

W. Zinth, M. C. Nuss, and W. Kaiser, Chem. Phys. Lett. 88, 257 (1982).
[Crossref]

J. Chem. Phys. (5)

C. L. Schosser and D. D. Dlott, J. Chem. Phys. 80, 1394 (1984).
[Crossref]

E. L. Chronister and D. D. Dlott, J. Chem. Phys. 79, 5286 (1983); E. L. Chronister, J. R. Hill, and D. D. Dlott, J. Chim. Phys. Phys. Chim. Biol. 82, 159 (1985).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 949 (1988).
[Crossref]

J. R. Hill, E. L. Chronister, T. -C. Chang, H. Kim, J. C. Postlewaite, and D. D. Dlott, J. Chem. Phys. 88, 2361 (1988).
[Crossref]

M. Nicol, M. Vernon, and J. T. Woo, J. Chem. Phys. 63, 1992 (1975).
[Crossref]

J. Chim. Phys. Phys. Chim. Biol. (1)

S. P. Velsko and R. M. Hochstrasser, J. Chim. Phys. Phys. Chim. Biol. 82, 153 (1985); J. Phys. Chem. 89, 2240 (1985).

Phys. Rev. Lett. (2)

C. B. Harris, H. Auweter, and S. M. George, Phys. Rev. Lett. 44, 737 (1980); S. M. George, H. Auweter, and C. B. Harris, J. Chem. Phys. 73, 5573 (1980).
[Crossref]

M. L. Geirnaert, G. M. Gale, and C. Flytzanis, Phys. Rev. Lett. 52, 815 (1984).
[Crossref]

Rev. Mod. Phys. (1)

A. Laubereau and W. Kaiser, Rev. Mod. Phys. 50, 608 (1978).
[Crossref]

Spectrochim. Acta Part A (1)

A. Bree and R. A. Kydd, Spectrochim. Acta Part A 26, 1791 (1970).
[Crossref]

Other (3)

G. R. Fleming, Chemical Applications of Ultrafast Spectroscopy (Oxford, New York, 1986), p. 45.

D. D. Dlott, in Laser Spectroscopy of Solids II, W. M. Yen, ed. (Springer-Verlag, Berlin, 1988), pp. 167–200.

S. Chen, X. Wen, and D. D. Dlott, “Low-temperature vibrational relaxation of high explosives” (submitted to J. Chem. Phys.

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Figures (5)

Fig. 1
Fig. 1

Schematic diagram of apparatus used for (a) conventional two-color picosecond-CARS measurements of transparent single crystals and (b) three-color picosecond-CARS backscattering of opaque or polycrystalline samples. In the two-color technique three different pulses are produced at the CARS frequency 2ω1ω2 (dashed lines). Scattered light from the two-pulse CARS signals interferes with the detection of the three-pulse signal. In the three-color configuration, the three-pulse CARS signal is at a unique wavelength ω1ω2 + ω3.

Fig. 2
Fig. 2

(a) Experimentally determined AC and XC functions of the two dye lasers and the Nd:YAG second-harmonic pulses. (b) Apparatus time-response functions for the two-color and three-color picosecond-CARS configurations.

Fig. 3
Fig. 3

Schematic timing diagram for various picosecond-CARS configurations. In (a) there is no jitter between the ω1 pump and the ω1 probe pulse. In (b) the longer Nd:YAG second-harmonic pulse is used for excitation. In (c) the longer pulse is used as the probe.

Fig. 4
Fig. 4

Experimental three-color picosecond-CARS data on the ~656-cm−1 symmetric stretching mode of polycrystalline CS2 ice. The semilog plot shows that the decays are exponential over a dynamic range greater than 200:1. The decay constants are a factor of 2 slower than those observed in single crystals,1 probably because of more efficient strain relief in the polycrystalline ice.

Fig. 5
Fig. 5

Three-color picosecond-CARS decays on naphthalene ν5 (~1385 cm−1) at 15 K. The sample was intentionally strained by grinding and compression. The semilog plot shows that the decay falls off faster than a computed exponential (solid curve), whereas purely exponential decays are observed in unstrained single crystals.

Tables (2)

Tables Icon

Table 1 Experimentally Determined Laser-Pulse Parameters

Tables Icon

Table 2 Three-Color Picosecond-CARS Instrument Response for Various Pulse Configurations

Equations (6)

Equations on this page are rendered with MathJax. Learn more.

C ( t d ) - - d t 12 d t P ( t 12 ) I 1 ( t ) I 2 ( t - t d - t 12 ) .
δ C 2 = δ 1 2 + δ 2 2 + δ 12 2 .
Q ( t ) - d t 12 P ( t 12 ) I 1 ( t ) I 2 ( t - t 12 ) .
1 δ Q 2 = 1 δ 1 2 + 1 δ 2 2 + δ 12 2 .
I CARS ( t d ) - - d t d t 13 P ( t 13 ) Q ( t ) I 3 ( t - t d - t 13 ) .
δ CARS = [ δ 1 2 ( δ 2 2 + δ 12 2 ) δ 1 2 + δ 2 2 + δ 12 2 + δ 3 2 + δ 13 2 ] 1 / 2 .

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