Abstract

The construction of a photoelectric Raman spectrometer is briefly described, and the procedure used to determine the intensities of Raman lines is given in detail. The relative intensities of the Raman lines of carbon tetrachloride, chloroform, and methylene chloride in the liquid state have been measured on a uniform scale. The values obtained for the individual molecules CCl4 and CHCl3 are in excellent agreement with those obtained previously by D. H. Rank [ J. Opt. Soc. Am. 37, 798 ( 1947)] using the photoelectric method. The whole range of intensities on a uniform scale for the three molecules are also in good general agreement with those obtained by Welsh, Crawford, Thomas, and Love [ Can. J. Phys. 30, 577 ( 1952)] in the gaseous phase using the photographic method. Only one out of thirteen strong lines has a significant intensity deviation of more than 15 percent from the mean values of the two sets of results. It is concluded that intensity measurements in the liquid phase for molecules with weak intermolecular forces may sometimes be adequate substitutes for the gaseous measurements that are strictly required for comparison with theoretical calculations.

© 1954 Optical Society of America

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References

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1953 (2)

D. A. Long, Proc. Roy. Soc. (London) A217, 203 (1953).
[Crossref]

H. J. Marrinan, J. Opt. Soc. Am. 43, 1211 (1953).
[Crossref]

1952 (3)

1951 (1)

L. A. Woodward and J. H. B. George, Proc. Phys. Soc. (London) B64, 780 (1951).
[Crossref]

1949 (5)

L. A. Woodward and D. A. Long, Trans. Faraday Soc. 45, 1131 (1949).
[Crossref]

E. F. Daly and G. B. B. M. Sutherland, Proc. Phys. Soc. (London) A62, 205 (1949).
[Crossref]

A. C. Menzies and J. Skinner, J. Sci. Instr. 26, 299 (1949).
[Crossref]

Miller, Long, Woodward, and Thompson, Proc. Phys. Soc. (London) A62, 401 (1949).
[Crossref]

J. Strong, J. Opt. Soc. Am. 39, 320 (1949).
[Crossref] [PubMed]

1947 (3)

1946 (1)

1945 (3)

F. F. Cleveland, J. Chem. Phys. 13, 101 (1945).
[Crossref]

M. Eliashevich and M. Wolkenstein, J. Phys. U.R.S.S. 9, 101 (1945).

M. Wolkenstein and M. Eliashevich, Acta Physicochim. U.R.S.S. 20, 524 (1945).

1944 (1)

Glockler, Haskin, and Patterson, J. Chem. Phys. 12, 349 (1944).
[Crossref]

1943 (1)

1942 (1)

1941 (1)

M. W. Wolkenstein, J. Phys. U.R.S.S. 5, 185 (1941).

1934 (1)

C. Placzek, Handbuch d. Radiologie VI, 2, 205 (1934).

Bender, P.

J. Y. Chien and P. Bender, J. Chem. Phys. 15, 376 (1947).
[Crossref]

Busing, W. R.

Chien, J. Y.

J. Y. Chien and P. Bender, J. Chem. Phys. 15, 376 (1947).
[Crossref]

Cleveland, F. F.

F. F. Cleveland, J. Chem. Phys. 13, 101 (1945).
[Crossref]

Coleman,

Crawford,

Welsh, Crawford, Thomas, and Love, Can. J. Phys. 30, 577 (1952).
[Crossref]

Daly, E. F.

E. F. Daly and G. B. B. M. Sutherland, Proc. Phys. Soc. (London) A62, 205 (1949).
[Crossref]

Eliashevich, M.

M. Wolkenstein and M. Eliashevich, Acta Physicochim. U.R.S.S. 20, 524 (1945).

M. Eliashevich and M. Wolkenstein, J. Phys. U.R.S.S. 9, 101 (1945).

Engstrom, R. W.

George, J. H. B.

L. A. Woodward and J. H. B. George, Proc. Phys. Soc. (London) B64, 780 (1951).
[Crossref]

Glockler,

Glockler, Haskin, and Patterson, J. Chem. Phys. 12, 349 (1944).
[Crossref]

Grimm,

Haskin,

Glockler, Haskin, and Patterson, J. Chem. Phys. 12, 349 (1944).
[Crossref]

Long,

Miller, Long, Woodward, and Thompson, Proc. Phys. Soc. (London) A62, 401 (1949).
[Crossref]

Long, D. A.

D. A. Long, Proc. Roy. Soc. (London) A217, 203 (1953).
[Crossref]

L. A. Woodward and D. A. Long, Trans. Faraday Soc. 45, 1131 (1949).
[Crossref]

Love,

Welsh, Crawford, Thomas, and Love, Can. J. Phys. 30, 577 (1952).
[Crossref]

Marrinan, H. J.

Menzies, A. C.

A. C. Menzies and J. Skinner, J. Sci. Instr. 26, 299 (1949).
[Crossref]

Miller,

Miller, Long, Woodward, and Thompson, Proc. Phys. Soc. (London) A62, 401 (1949).
[Crossref]

Patterson,

Glockler, Haskin, and Patterson, J. Chem. Phys. 12, 349 (1944).
[Crossref]

Pfister,

Placzek, C.

C. Placzek, Handbuch d. Radiologie VI, 2, 205 (1934).

Rank,

Rank, D. H.

Skinner, J.

A. C. Menzies and J. Skinner, J. Sci. Instr. 26, 299 (1949).
[Crossref]

Strong, J.

Sutherland, G. B. B. M.

E. F. Daly and G. B. B. M. Sutherland, Proc. Phys. Soc. (London) A62, 205 (1949).
[Crossref]

Thomas,

Welsh, Crawford, Thomas, and Love, Can. J. Phys. 30, 577 (1952).
[Crossref]

Thompson,

Miller, Long, Woodward, and Thompson, Proc. Phys. Soc. (London) A62, 401 (1949).
[Crossref]

Walsh, A.

Welsh,

Welsh, Crawford, Thomas, and Love, Can. J. Phys. 30, 577 (1952).
[Crossref]

Wiegand, R. V.

Wolkenstein, M.

M. Eliashevich and M. Wolkenstein, J. Phys. U.R.S.S. 9, 101 (1945).

M. Wolkenstein and M. Eliashevich, Acta Physicochim. U.R.S.S. 20, 524 (1945).

Wolkenstein, M. W.

M. W. Wolkenstein, J. Phys. U.R.S.S. 5, 185 (1941).

Woodward,

Miller, Long, Woodward, and Thompson, Proc. Phys. Soc. (London) A62, 401 (1949).
[Crossref]

Woodward, L. A.

L. A. Woodward and J. H. B. George, Proc. Phys. Soc. (London) B64, 780 (1951).
[Crossref]

L. A. Woodward and D. A. Long, Trans. Faraday Soc. 45, 1131 (1949).
[Crossref]

Acta Physicochim. U.R.S.S. (1)

M. Wolkenstein and M. Eliashevich, Acta Physicochim. U.R.S.S. 20, 524 (1945).

Can. J. Phys. (1)

Welsh, Crawford, Thomas, and Love, Can. J. Phys. 30, 577 (1952).
[Crossref]

Handbuch d. Radiologie (1)

C. Placzek, Handbuch d. Radiologie VI, 2, 205 (1934).

J. Chem. Phys. (3)

F. F. Cleveland, J. Chem. Phys. 13, 101 (1945).
[Crossref]

Glockler, Haskin, and Patterson, J. Chem. Phys. 12, 349 (1944).
[Crossref]

J. Y. Chien and P. Bender, J. Chem. Phys. 15, 376 (1947).
[Crossref]

J. Opt. Soc. Am. (9)

J. Phys. U.R.S.S. (2)

M. W. Wolkenstein, J. Phys. U.R.S.S. 5, 185 (1941).

M. Eliashevich and M. Wolkenstein, J. Phys. U.R.S.S. 9, 101 (1945).

J. Sci. Instr. (1)

A. C. Menzies and J. Skinner, J. Sci. Instr. 26, 299 (1949).
[Crossref]

Proc. Phys. Soc. (London) (3)

Miller, Long, Woodward, and Thompson, Proc. Phys. Soc. (London) A62, 401 (1949).
[Crossref]

E. F. Daly and G. B. B. M. Sutherland, Proc. Phys. Soc. (London) A62, 205 (1949).
[Crossref]

L. A. Woodward and J. H. B. George, Proc. Phys. Soc. (London) B64, 780 (1951).
[Crossref]

Proc. Roy. Soc. (London) (1)

D. A. Long, Proc. Roy. Soc. (London) A217, 203 (1953).
[Crossref]

Trans. Faraday Soc. (1)

L. A. Woodward and D. A. Long, Trans. Faraday Soc. 45, 1131 (1949).
[Crossref]

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Figures (3)

F. 1
F. 1

The optical system of the photoelectric recording Raman spectrometer: C1—condensing lens between Raman tube and entrance slit; C2—collimating lens of the spectrometer; E1—entrance slit; E2—exit slit; G—grating; M—plane mirror; P—photo-multiplier; and S—scanning motor.

F. 2
F. 2

(A) Photoelectric Raman spectrum of CCl4 (slit width, 10 cm−1: time of scan, 40 min); (B) 459 cm−1 Raman line of CCl4 run slowly for intensity measurements; and (C) 762, 791 cm−1 doublet of CCl4 run slowly.

F. 3
F. 3

Photoelectric Raman spectrum of methylene chloride (CH2Cl2).

Tables (1)

Tables Icon

Table I The relative intensities of the Raman lines of some chlorinated methanes excited by 4358-A mercury radiation.

Equations (4)

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I red = I exp ( ν 0 ν ) 4 ( 1 e h ν / k T ) ,
Intensity ( CH 2 Cl 2 : 700 cm 1 ) Intensity ( CCl 4 : 459 cm 1 ) = 0.47 , Intensity ( CHCl 3 : 667 cm 1 ) Intensity ( CCl 4 : 459 cm 1 ) = 0.63 .
100 ( ν 2 ν 1 ) ( ν 2 + ν 1 )
100 ( I 2 I 1 ) ( I 2 + I 1 )