The molecules CH3OH, CD3OH, and CH3OD have been investigated by photoionization mass spectrometry from the onset of dissociative ionization to 20 eV. The process forming methyl ion and hydroxyl radical is shown to be direct, rather than statistical. Near threshold, the process involving molecular hydrogen elimination is shown to lead to the structure HCOH+, rather than H2CO+. Removal of an H atom leads predominantly to CH2OH+, although some evidence exists for a CH3O+ structure at higher energy. Similarly, the structure HCO+ is seen to be much more prevalent than COH+, but the latter may be formed with increasing probability at higher energy. Some astrophysical implications regarding the formation of CH2O in dense interstellar clouds are discussed.

1.
K. M. A.
Refaey
and
W. A.
Chupka
,
J. Chem. Phys.
48
,
5205
(
1968
).
2.
V. K.
Potapov
and
V. V.
Sorokin
,
Khim. Vys. Energ.
4
,
355
(
1970
).
3.
I.
Omura
,
T.
Kaneko
,
Y.
Yamada
, and
K.
Tanaka
,
J. Phys. Soc. Jpn.
27
,
981
(
1969
).
4.
P.
Warneck
,
Z. Naturforsch. Teil A
26
,
2047
(
1971
).
5.
E. V.
Puttkamer
,
Z. Naturforsch. Teil A
25
,
1062
(
1970
).
6.
B.
Brehm
,
V.
Fuchs
, and
P.
Kebarle
,
Int. J. Mass Spectrom. Ion Phys.
6
,
279
(
1971
).
7.
J.
Berkowitz
and
W. A.
Chupka
,
J. Chem. Phys.
45
,
1287
(
1966
).
8.
ANL E350S‐1, “Smoothing by Cubic Splines,” available from Applied Mathematics Division, Argonne National Laboratory.
9.
J. Berkowitz, Photoabsorption, Photoionization, and Photoelectron Spectroscopy, (Academic, New York, 1979), (in press).
10.
The photoelectron spectrum shown here was taken in the laboratory of Prof. W. C. Price, and was published in Photoelectron Spectroscopy by J. H. D. Eland, (Butterworths London 1974), p. 22.
11.
M. Vestal and G. Lerner, “Fundamental Studies Relating to the Radiation Chemistry of Small Molecules,” Aerospace Research Laboratories Rep. ARL 67–0114 (1967).
12.
S.
Ikuta
,
K.
Yoshihara
, and
T.
Shiokawa
,
Mass Spectroscopy
22
,
233
(
1974
);
S.
Ikuta
,
K.
Yoshihara
, and
T.
Shiokawa
,
23
,
61
(
1975
).
13.
B.‐O.
Jonsson
and
J.
Lind
,
J. Chem. Soc. Faraday Trans. 2
72
,
906
(
1976
).
14.
P.
Wilmenius
and
E.
Lindholm
,
Arkiv Fysik
21
,
97
(
1962
).
15.
M. B.
Robin
and
N. A.
Kuebler
,
J. Electron Spectrosc. Relat. Phenom.
1
,
13
(
1972
).
16.
K.
Hiraoka
and
P.
Kebarle
,
J. Chem. Phys.
63
,
1688
(
1975
).
17.
J. H. Callomon, E. Hirota, K. Kuchitsu, W. J. Lafferty, A. G. Maki, and C. S. Pote, Structure Data of Free Polyatomic Molecules, Landolt‐Börnstein Tables, New Series, Group II (Springer‐Verlag, Berlin 1976).
18.
H. B.
Jansen
and
P.
Ros
,
Chem. Phys. Lett.
3
,
140
(
1969
).
19.
S.
Forsén
and
B.
Roos
,
Chem. Phys. Lett.
6
,
128
(
1970
).
20.
P. J.
Bruna
,
S. D.
Peyerimhoff
, and
R. J.
Buenker
,
Chem. Phys.
10
,
323
(
1975
).
21.
See, for example,
K. F.
Freed
,
Topics in Appl. Phys.
15
,
23
(
1976
).
22.
J. H. D.
Eland
,
R.
Frey
,
A.
Kuestler
,
H.
Schulte
, and
B.
Brehm
,
Int. J. Mass Spectrom. Ion Phys.
22
,
155
(
1976
).
23.
M. A.
Haney
,
J. C.
Patel
, and
E. F.
Hayes
,
J. Chem. Phys.
53
,
4105
(
1970
).
24.
F. C.
Fehsenfeld
,
D. B.
Dunkin
, and
E. E.
Ferguson
,
Astrophys. J.
188
,
43
(
1974
).
25.
E.
Herbst
and
W.
Klemperer
,
Astrophys. J.
185
,
505
(
1973
).
26.
A.
Dalgarno
,
M.
Oppenheimer
, and
J. H.
Black
,
Nature (London) Phys. Sci.
245
,
100
(
1973
).
27.
W.
Langer
,
Astrophys. J.
206
,
699
(
1976
).
28.
G. F. Mitchell, J. L. Ginsburg, and P. J. Kuntz, Astrophys. J. (submitted for publication).
29.
F.
Arnold
,
D.
Krankowsky
, and
K. H.
Marien
,
Nature (London)
267
,
30
(
1977
).
30.
L. E.
Snyder
and
D.
Buhl
,
Nature (London)
227
,
862
(
1970
).
L. E.
Snyder
and
D.
Buhl
,
Bull. Am. Astron. Soc.
3
,
388
(
1971
).
31.
L. E.
Snyder
,
J. M.
Hollis
,
B. L.
Ulich
,
F. J.
Lovas
, and
D.
Buhl
,
Bull. Am. Astron. Soc.
7
,
497
(
1975
).
32.
E.
Herbst
and
W.
Klemperer
,
Astrophys. J.
207
,
110
(
1976
).
33.
W. A.
Lathan
,
L. A.
Curtiss
,
W. J.
Hehre
,
J. B.
Lisle
, and
J. A.
Pople
,
Prog. Phys. Org. Chem.
11
,
175
(
1974
).
34.
T. H. Dunning, Jr. (private communication).
This content is only available via PDF.
You do not currently have access to this content.