The photoionization yields of CH3Cl, CH2Cl2, CHCl3, CCl4, and CBr4 have been measured in the 10–13.5 eV energy range. Ionization potentials and fragment appearance potentials derived from a detailed study of the hot band contribution at 300°K have been obtained. Although is apparently unstable, we have found that is stable. Fragmentation of the chlorinated and brominated methanes in the energy range studied appears to be limited to halogen loss, even though hydrogen loss is in certain cases energetically favored. An argument based on the symmetry of the fragments and the transition state producing these fragments is proposed to account for this observation.
REFERENCES
1.
J. L. Franklin, J. G. Dillard, H. M. Rosenstock, J. T. Herron, K. Drasl, and F. H. Field, “Ionization Potentials, Appearance Potentials and Heats of Formation of Gaseous Positive Ions,” NBS‐NSRD Publication, U.S. Government Printing Office, Washington, D.C., No. 26 (1969).
2.
3.
4.
5.
R. N.
Dixon
, J. N.
Murrell
and B.
Narayan
, Mol. Phys.
20
, 611
(1971
).6.
7.
8.
9.
10.
11.
R. H.
Martin
, F. W.
Lampe
, and R. W.
Taft
, J. Am. Chem. Soc.
88
, 1353
(1966
).12.
J. D.
Morrison
and A. J. C.
Nicholson
, J. Chem. Phys.
20
, 1021
(1952
).13.
14.
15.
S.
Tsuda
, C. E.
Melton
, and W. H.
Hamill
, J. Chem. Phys.
41
, 689
(1964
).16.
17.
V. H.
Dibeler
and R. M.
Reese
, J. Res. Natl. Bur. Stand.
54
, 127
(1965
).18.
19.
20.
D. W. Turner, C. Baker, A. D. Baker, and C. R. Brundle, Molecular Photoelectron Spectroscopy (Wiley, New York, 1970).
21.
22.
23.
J. B.
Farmer
, I. H. S.
Henderson
, F. P.
Lossing
, and D. G. H.
Marsden
, J. Chem. Phys.
24
, 348
(1956
).24.
25.
26.
J. L.
Ragle
, I. A.
Stenhouse
, D. C.
Frost
, and C. A.
McDowell
, J. Chem. Phys.
53
, 178
(1970
).27.
28.
29.
30.
M.
Baldwin
, A.
Maccoll
, and S. I.
Miller
, J. Am. Chem. Soc.
86
, 4498
(1964
).31.
32.
A. W.
Potts
, H. J.
Lempha
, D. G.
Streets
, and W. C.
Price
, Phil. Trans. Soc. Lond. A
268
, 59
(1970
).33.
G. H. Herzberg, Molecular Spectra and Molecular Structure (Van Nostrand, Princeton, NJ, 1967), Vol. III, p. 346.
34.
F. A.
Elder
, C.
Giese
, B.
Steiner
, and M.
Inghram
, J. Chem. Phys.
36
, 3292
(1962
).35.
36.
37.
M.
Kraus
, J. A.
Walker
, and V. H.
Dibeler
, J. Res. Natl. Bur. Stand. A
72
, 281
(1968
).38.
The data are summarized and related to the photoelectron spectra of the fluorinated methanes by
C. R.
Brundle
, M. B.
Robin
, and H.
Basch
, J. Chem. Phys.
53
, 2196
(1970
).39.
40.
M. L. Vestal, Fundamental Processes in Radiation Chemistry, edited by P. Ausloos (Interscience, New York, 1968), p. 82.
41.
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