Coherent Anti-Stokes Raman Spectroscopy of the Stretching Vibrations of the Water Isotopomers

Abstract

Coherent anti-Stokes Raman spectroscopy (CARS) has been employed to study the v₁ band of H₂O, v₁ band of D_zO, and v₁ and v₃ bands of HOD in the gas phase at room temperature and at moderate resolution. These molecules are characterized by a complicated spectrum which is not completely rotationally resolved. A method for the deconvolution of incompletely resolved CARS spectra has been utilized, in which a Boltzmann population distribution is assumed. The calculated spectrum nearly exactly reproduces the observed spectrum and allows assignment of the rotational transitions which are observed in the spectra. All the transitions that appear in these spectra belong to the isotropic Q branches. The CARS spectra of D₂O and HOD are studied here for the first time.

Keywords

Raman spectroscopy CARS

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References

See, for example, special issues of Applied Physics B 50, pp. 441–462 and B 51, pp. 9–62 (1990).

Valentini

J. J.

, in Laser Spectroscopy and its Applications, Opt. Eng., Vol. 11, Radziemsky

L. J.

Solarz

R. W.

and Paisner

J. A

, Eds. (Marcel Dekker, New York, 1987), p. 507; Valentini

J. J.

, in Spectrometric Techniques, Vanasse

G. A.

Ed. (Academic Press, New York, 1985), Vol. 4, p. 1.

Druet

S. A.

and Taran

J. P

, Prog. Quantum. Electron. 7, 1 (1981).

Nibler

J. W.

and Knighten

G. V

, in Raman Spectroscopy of Gases and Liquids, Topics in Applied Physics, Vol. 11, Weber

Ed. (Springer, Berlin/Heidelberg/New York, 1979), p. 253.

Hall

R. J.

, Combust. Flame 35, 47 (1979).

Grisch

Péalat

Collin

Taran

J. P.

Bar

Heflinger

and Rosenwaks

, Appl. Phys. Lett. 59, 3516 (1991).

Valentini

J. J.

Aker

P. M.

Germann

G. J.

and Huh

Y-D

, Faraday Discuss. Chem. Soc. 91, 173 (1991); Gerrity

D. P.

and Valentini

J. J

, J. Chem. Phys. 83, 2207 (1985); Gerrity

D. P.

and Valentini

J. J

, J. Chem. Phys. 83, 1323 (1985).

Cohen

David

Arusi-Parpar

Bar

Rosenwaks

and Valentini

J. J

, in Mode Selective Chemistry, Jortner

Levine

R. D.

and Pullman

, Eds. (Kluwer, Dordrecht, 1991), p. 227; Bar

Cohen

David

Arusi-Parpar

Rosenwaks

and Valentini

J. J

, J. Physique 1, 7 (1991); Bar

Cohen

David

Arusi-Parpar

Rosenwaks

and Valentini

J. J

, J. Chem. Phys. 95, 3341 (1991); Bar

Cohen

David

Rosenwaks

and Valentini

J. J

, J. Chem. Phys. 93, 2146 (1990).

David

Strugano

Bar

and Rosenwaks

, unpublished results.

10.

Herzberg

, Molecular Spectra and Molecular Structure II: Infrared and Raman Spectra (D. Van Nostrand, New York, 1945).

11.

Murphy

W. F.

, Mol. Phys. 36, 727 (1978); Murphy

W. F.

, J. Chem. Phys. 67, 5877 (1977); Murphy

W. F.

, Mol. Phys. 33, 1701 (1977).

12.

Penney

C. M.

and Lapp

, J. Opt. Soc. Am. 66, 422 (1976); Bribes

J. L.

Gaufres

Monan

Lapp

and Penney

C. M

, Appl. Phys. Lett. 28, 336 (1976).

13.

Bubkin

S. B.

Gladkov

S. M.

Morozov

V. B.

and Smirnov

V. B

, Opt. Spectrosc. (USSR) 62, 214 (1987).

14.

(a) Hall

R. J.

and Shirley

J. A

, Appl. Spectrosc. 37, 196 (1983); (b) Hall

R. J.

Shirley

J. A.

and Eckbreth

A. C

, Opt. Lett. 4, 87 (1979).

15.

Greenhalgh

D. A.

and Rahn

L. A

, J. Raman Spectrosc. 21, 847 (1990); Rahn

L. A.

and Greenhalgh

D. A

, J. Mol. Spectrosc. 119, 11 (1986).

16.

Anda

A. A.

Phillips

D. L.

and Valentini

J. J

, J. Chem. Phys. 85, 1719 (1986).

17.

Yuratich

M. A.

, Mol. Phys. 38, 625 (1979).

18.

Yuratich

M. A.

and Hanna

D. C

, Mol. Phys. 33, 671 (1977).

19.

Murphy

W. F.

, J. Raman Spectrosc. 11, 339 (1981).

20.

Hills

G. W.

Foster

R. B.

and Jones

W. J

, Mol. Phys. 33, 1571 (1977).

21.

Weber

, in The Raman Effect, Anderson

Ed. (Marcel Dekker, New York, 1973), Vol. 2, p. 543.

22.

Brodersen

, in Raman Spectroscopy of Gases and Liquids, Topics in Applied Physics, Vol. 11, Weber

Ed. (Springer, Berlin/Heidelberg/New York, 1979), p. 7.

23.

Frunder

Angstl

Illig

Schrotter

H. W.

Lechuga-Fossat

Flaud

J. M.

Camy-Peyret

and Murphy

W. F

, Can. J. Phys. 63, 1189 (1985).

24.

Montero

, J. Chem. Phys. 79, 4091 (1983).

25.

Flaud

J. M.

and Camy-Peyret

, J. Mol. Spectrosc. 51, 142 (1974).

26.

Papineau

Flaud

J. M.

Camy-Peyret

and Guelachvili

, J. Mol. Spectrosc. 87, 219 (1981).

27.

Version 2.10 (ASYST Software Tecnologies Inc., Rochester, New York, 1988).

28.

Flaud

J. M.

Camy-Peyret

and Maillard

J. P

, Mol. Phys. 32, 499 (1976).

29.

Papineau

Camy-Peyret

Flaud

J. M.

and Guelachvili

, J. Mol. Spectrosc. 92, 451 (1982).

30.

Toth

R. A.

and Brault

J. W

, Appl. Opt. 22, 908 (1983).

31.

Arnold

J. O.

Whiting

E. E.

and Lyle

G. C

, J. Quant. Spectrosc. Radiant. Transfer. 9, 775 (1969).

32.

Hartmann

J. M.

, J. Mol. Spectrosc. 127, 35 (1988).

33.

Constantinides

, Applied Numerical Methods with Personal Computers (McGraw-Hill, New York, 1987), p. 343.

34.

Benedict

W. S.

Gailar

and Plyler

E. K

, J. Chem. Phys. 24, 1139 (1956).