From high resolution photoionization mass spectrometric data on normal and isotopically substituted N2O it is concluded that the formation of NO+ below the à state of N2O+ but above the thermochemical threshold involves the calculated but hitherto unobserved 4A″ state. This state decays to NO+ from low vibrational levels, and mainly to O+ from higher levels. The O+ ion is a more important product of N2O photodissociation than previously thought. The B̃ state of N2O+ is shown to decompose to NO+ and N2+ and the C̃ state to NO+, N2+, N+, and O+. The branching in autoionization from the Ã, B̃, and C̃ Rydberg series to states of different continua has been determined and is found to depend more on the type of series than on the principal quantum number. The shapes of the resonances are strikingly different in the different final channels. The relevance of these findings to ionospheric O++N2 reaction is discussed.

1.
V. H.
Dibeler
,
J. A.
Walker
, and
S. K.
Liston
,
J. Res. Natl. Bur. Stand. Sect. A
71
,
371
(
1967
).
2.
P.
Coppens
,
J.
Smets
,
M. G.
Fishel
, and
J.
Drowart
,
Int. J. Mass Spectrom. Ion Phys.
14
,
57
(
1974
).
3.
E. G. C.
Stueckelberg
and
H. D.
Smith
,
Phys. Rev.
36
,
478
(
1930
);
J. E.
Collin
and
F. P.
Lossing
,
J. Chem. Phys.
28
,
900
(
1958
);
R. K.
Curran
and
R. E.
Fox
,
J. Chem. Phys.
34
,
1590
(
1961
).
4.
V. H.
Dibeler
,
J. Chem. Phys.
47
,
2191
(
1967
).
5.
Y.
Tanaka
,
A. S.
Jursa
, and
F. J.
LeBlanc
,
J. Chem. Phys.
32
,
1205
(
1960
).
6.
J. H.
Callomon
and
F.
Creutzberg
,
Philos. Trans. R. Soc. London
227
,
157
(
1974
).
7.
E.
Lindholm
,
Ark. Fys.
40
,
129
(
1969
).
8.
D. W. Turner, C. Baker, A. D. Baker, and C. R. Brundle, Molecular Photoelectron Spectroscopy (Wiley‐Interscience, London, 1970).
9.
J. H. D.
Eland
,
Int. J. Mass Spectrom. Ion Phys.
12
,
389
(
1973
).
10.
R. J.
Coleman
,
J. S.
Delderfield
, and
B. G.
Reuben
,
Int. J. Mass Spectrom. Ion Phys.
2
,
25
(
1969
).
11.
A. S.
Newton
and
A. F.
Sciamanna
,
J. Chem. Phys.
52
,
327
(
1970
).
12.
W. H.
Smith
,
J. Chem. Phys.
51
,
3410
(
1969
).
13.
G. M.
Begun
and
L.
Landau
,
J. Chem. Phys.
35
,
547
(
1961
).
14.
R. G.
Orth
and
R. C.
Dunbar
,
J. Chem. Phys.
66
,
1616
(
1977
).
15.
K. R.
Ryan
,
J. Chem. Phys.
57
,
271
(
1972
).
16.
J. C.
Lorquet
and
C.
Cadet
,
Int. J. Mass Spectrom. Ion Phys.
7
,
245
(
1971
).
17.
A.
Pipano
and
J. J.
Kaufman
,
J. Chem. Phys.
56
,
5258
(
1972
).
18.
D. G.
Hopper
,
Chem. Phys. Lett.
31
,
446
(
1975
).
19.
A. D. McLean and M. Yoshimine, Tables of Linear Molecule Wavefunctions (IBM, San Jose, 1967).
20.
B.
Brehm
,
R.
Frey
,
A.
Küstler
, and
J. H. D.
Eland
,
Int. J. Mass Spectrom. Ion Phys.
13
,
257
(
1974
).
21.
H.
Hertz
,
H.‐N.
Jochims
, and
W.
Sroka
,
J. Phys. B
1
,
L548
(
1974
).
22.
G. R.
Cook
,
P. H.
Metzger
, and
M.
Ogawa
,
J. Opt. Soc. Am.
58
,
129
(
1968
).
23.
U.
Fano
,
Phys. Rev.
124
,
1866
(
1961
).
24.
M. J.
Weiss
,
Chem. Phys. Lett.
39
,
250
(
1976
).
25.
D. B.
Dunkin
,
F. C.
Fehsenfeld
,
A. L.
Schmeltekopf
, and
E. E.
Ferguson
,
J. Chem. Phys.
49
,
1365
(
1968
).
26.
M.
McFarland
,
D. L.
Albritton
,
F. C.
Fehsenfeld
,
E. E.
Ferguson
, and
A. L.
Schmeltekopf
,
J. Chem. Phys.
59
,
6620
(
1973
).
27.
G. P. K.
Smith
and
R. J.
Cross
, Jr.
,
J. Chem. Phys.
60
,
2125
(
1974
).
28.
R. H.
Neynaber
and
G. D.
Magnusson
,
J. Chem. Phys.
58
,
4586
(
1974
).
29.
J. J.
Leventhal
,
J. Chem. Phys.
54
,
5102
(
1971
).
30.
D. G. Hopper (private communication).
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