We present the first measurements of ion rotational distributions for photoionization over an extended range [0≤EK≤200 eV for N2 (2σ−1u) and 3≤EK≤125 eV for CO (4σ−1)]. The N2 ion rotational distributions are seen to change dramatically over this energy range, indicating that characteristically molecular behavior of the photoelectron persists far from ionization threshold. In addition, the N2 and CO results show a strikingly different dependence on energy. Although differences are expected due to the absence of a center of symmetry in CO, detailed calculations reveal that this behavior arises from the presence of Cooper minima in the 2σukσg continuum in the case of N2 and from an f‐wave shape resonance in the 4σ→kσ channel in CO. Agreement between measured and calculated ion rotational distributions is excellent. The N2 results are also compared with electron bombardment ionization data. This comparison demonstrates that previous interpretations of electron bombardment data are prone to errors.

1.
L.
Äsbrink
,
Chem. Phys. Lett.
7
,
549
(
1970
).
2.
A. D.
Buckingham
,
B. J.
Orr
, and
J. M.
Sichel
,
Philos. Trans. R. Soc. London Sect. A
268
,
147
(
1970
).
3.
D.
Dill
,
Phys. Rev. A
6
,
160
(
1972
).
4.
J. E.
Pollard
,
D. J.
Trevor
,
J. E.
Reutt
,
Y. T.
Lee
, and
D. A.
Shirley
,
J. Chem. Phys.
77
,
34
(
1982
).
5.
S. T.
Pratt
,
P. M.
Dehmer
, and
J. L.
Dehmer
,
J. Chem. Phys.
78
,
4315
(
1983
).
6.
W. G.
Wilson
,
K. S.
Viswanathan
,
E.
Sekreta
, and
J. P.
Reilly
,
J. Phys. Chem.
88
,
672
(
1984
).
7.
C. H.
Greene and Ch. Jungen
,
Adv. At. Mol. Phys.
21
,
51
(
1985
).
8.
E. D.
Poliakoff
,
J. C. K.
Chan
, and
M. G.
White
,
J. Chem. Phys.
85
,
6232
(
1986
).
9.
S. N.
Dixit
and
V.
McKoy
,
Chem. Phys. Lett.
128
,
49
(
1986
).
10.
R. G.
Tonkyn
,
J. W.
Winniczek
, and
M. G.
White
,
Chem. Phys. Lett.
164
,
137
(
1989
).
11.
J.
Xie
and
R. N.
Zare
,
Chem. Phys. Lett.
159
,
399
(
1989
).
12.
H.
Lefebvre-Brion
,
Chem. Phys. Lett.
171
,
377
(
1990
).
13.
M. S.
Child and Ch. Jungen
,
J. Chem. Phys.
93
,
7756
(
1990
).
14.
R. D.
Gilbert
and
M. S.
Child
,
Chem. Phys. Lett.
187
,
153
(
1991
).
15.
K.
Müller-Dethlefs
and
E. W.
Schlag
,
Annu. Rev. Phys. Chem.
42
,
109
(
1991
).
16.
F.
Merkt
and
T. P.
Softley
,
J. Chem. Phys.
96
,
4149
(
1992
).
17.
G. P.
Bryant
,
Y.
Jiang
,
M.
Martin
, and
E. R.
Grant
,
J. Phys. Chem.
96
,
6875
(
1992
).
18.
W.
Kong
,
D.
Rodgers
,
J. W.
Hepburn
,
K.
Wang
, and
V.
McKoy
,
J. Chem. Phys.
99
,
3159
(
1993
).
19.
R. T.
Wiedmann
,
M. G.
White
,
K.
Wang
, and
V.
McKoy
,
J. Chem. Phys.
100
,
4738
(
1994
).
20.
J. A.
Blush
,
P. C.
Chen
,
R. T.
Wiedmann
, and
M. G.
White
,
J. Chem. Phys.
98
,
3557
(
1993
).
21.
I.
Fischer
,
A.
Lochschmidt
,
A.
Strobel
,
G.
Niedner-Schatteburg
,
K.
Müller-Dethlefs
, and
V.
Bondybey
,
J. Chem. Phys.
94
,
3592
(
1993
).
22.
K.
Wang
and
V.
McKoy
,
J. Chem. Phys.
95
,
4977
(
1991
).
23.
J. L. Dehmer, D. Dill, and A. C. Parr, in Photophysics and Photochemistry in the Vacuum Ultraviolet, edited by S. P. McGlynn, G. L. Findley, and R. H. Heubner (Reidel, Dordrecht, Holland, 1985), p. 341.
24.
J. L. Dehmer, A. C. Parr, and S. H. Southworth, in Handbook on Synchro tron Radiation, edited by G. V. Marr (North-Holland, Amsterdam, 1987), Vol. II.
25.
P. W. Langhoff, in Resonances in Electron-Molecule Scattering, van der Waals Complexes and Reactive Chemical Dynamics, edited by D. G. Truhlar, ACS Symp. Ser. No. 263 (American Chemical Society, Washington, DC, 1984).
26.
J. W.
Gallagher
,
C. E.
Brion
,
J. A. R.
Samson
, and
P. W.
Langhoff
,
J. Chem. Phys. Ref Data
17
,
9
(
1988
).
27.
J. W.
Cooper
,
Phys. Rev.
128
,
681
(
1962
).
28.
S. T.
Manson
and
J. W.
Cooper
,
Phys. Rev.
165
,
126
(
1968
).
29.
H. C.
Choi
,
R. M.
Rao
,
A. G.
Mihill
,
S.
Kakar
,
E. D.
Poliakoff
,
K.
Wang
, and
V.
McKoy
,
Phys. Rev. Lett.
72
,
44
(
1994
).
30.
E. D. Poliakoff, Chem. Rev. (to be published).
31.
E. D. Poliakoff, in Vacuum Ultraviolet Photoionization and Photodissociation of Molecules and Clusters, edited by C. Y. Ng (World Scientific, Singapore, 1991).
32.
E. D.
Poliakoff
,
S.
Kakar
, and
R. A.
Rosenberg
,
J. Chem. Phys.
96
,
2740
(
1992
).
33.
K.
Wang
and
V.
McKoy
,
J. Chem. Phys.
95
,
7872
(
1991
).
34.
K. S.
Viswanathan
,
E.
Sekreta
,
E. R.
Davidson
, and
J. P.
Reilly
,
J. Phys. Chem.
90
,
5078
(
1986
).
35.
K. S.
Viswanathan
,
E.
Sekreta
, and
J. P.
Reilly
,
J. Phys. Chem.
90
,
5658
(
1986
).
36.
X.
Song
,
E.
Sekreta
,
J. P.
Reilly
,
H.
Rudolph
, and
V.
McKoy
,
J. Chem. Phys.
91
,
6062
(
1989
).
37.
S.
Kakar
,
H. C.
Choi
, and
E. D.
Poliakoff
,
J. Chem. Phys.
97
,
6998
(
1992
).
38.
H.
Rudolph
and
V.
McKoy
,
J. Chem. Phys.
91
,
2235
(
1989
).
39.
K.
Wang
,
J. A.
Stephens
, and
V.
McKoy
,
J. Chem. Phys.
95
,
6456
(
1991
).
40.
M.
Braunstein
,
V.
McKoy
,
S. N.
Dixit
,
R. G.
Tonkyn
, and
M. G.
White
,
J. Chem. Phys.
93
,
5345
(
1990
).
41.
E.
de Beer
,
M.
Born
,
C. A.
de Lange
, and
N. P. C.
Westwood
,
Chem. Phys. Lett.
186
,
40
(
1991
).
42.
E.
de Beer
,
M. P.
Koopmans
,
C. A.
de Lange
,
Y.
Wang
, and
W. A.
Chupka
,
J. Chem. Phys.
94
,
7634
(
1991
).
43.
E.
de Beer
,
C. A.
de Lange
,
J. A.
Stephens
,
K.
Wang
, and
V.
McKoy
,
J. Chem. Phys.
95
,
714
(
1991
).
44.
W. A.
Chupka
,
J. Chem. Phys.
98
,
4520
(
1992
).
45.
K. L.
Reid
,
D. J.
Leahy
, and
R. N.
Zare
,
Phys. Rev. Lett.
68
,
3527
(
1992
).
46.
S. W.
Allendorf
,
D. J.
Leahy
,
D. C.
Jacobs
, and
R. N.
Zare
,
J. Chem. Phys.
91
,
2216
(
1989
).
47.
M.
Mahalingam
,
K.
Lee
, and
D. M.
Hanson
,
J. Chem. Phys.
98
,
5239
(
1993
).
48.
K. J.
Randall
,
A. L. D.
Kilcoyne
,
H. M.
Köppe
,
J.
Feldhau
,
A. M.
Bradshaw
,
J. E.
Rubensson
,
W.
Eberhardt
,
Z.
Xu
,
P. D.
Johnson
, and
Y.
Ma
,
Phys. Rev. Lett.
71
,
1156
(
1993
).
49.
C. T.
Chen
,
Y.
Ma
, and
F.
Sette
,
Phys. Rev. A
40
,
6737
(
1989
).
50.
J. D.
Bozek
,
G. M.
Bancroft
,
J. N.
Cutler
, and
K. H.
Tan
,
Phys. Rev. Lett.
65
,
2757
(
1990
).
51.
A.
Niehaus
and
M. W.
Ruf
,
Chem. Phys. Lett.
11
,
55
(
1971
).
52.
P.
Baltzer
,
L.
Karlsson
, and
B.
Wannberg
,
Phys. Rev. A
46
,
315
(
1992
).
53.
M. G. White, in Highly Resolved Laser Photoionization and Photoelectron Studies, edited by I. Powis (Wiley, New York, 1995).
54.
K. Müller-Dethlefs, in Highly Resolved Laser Photoionization and Photo- electron Studies, edited by I. Powis (Wiley, New York, 1995).
55.
E. R. Grant, in Highly Resolved Laser Photoionization and Photoelectron Studies, edited by I. Powis (Wiley, New York, 1995).
56.
T. P. Softley, in Highly Resolved Laser Photoionization and Photoelectron Studies, edited by I. Powis (Wiley, New York, 1995).
57.
K.
Wang
,
J. A.
Stephens
, and
V.
McKoy
,
J. Phys. Chem.
97
,
9874
(
1993
).
58.
R. T.
Wiedmann
,
M. G.
White
,
K.
Wang
, and
V.
McKoy
,
J. Chem. Phys.
98
,
7673
(
1993
).
59.
A.
Strobel
,
I.
Fischer
,
J.
Staeker
,
G.
Nieder-Schatteburg
,
K.
Müller-Dethlefs
, and
V.
Bondybey
,
J. Chem. Phys.
97
,
2332
(
1991
).
60.
E. R.
Grant
and
M. G.
White
,
Nature (London)
354
,
249
(
1991
).
61.
M.-T.
Lee
,
K.
Wang
,
V.
McKoy
,
R. G.
Tonkyn
,
R. T.
Wiedmann
,
E. R.
Grant
, and
M. G.
White
,
J. Chem. Phys.
96
,
7848
(
1992
).
62.
X.
Zhang
,
J. M.
Smith
, and
J. L.
Knee
,
J. Chem. Phys.
99
,
3133
(
1993
).
63.
T.
Baumert
,
R.
Thalweiser
, and
G.
Gerber
,
Chem. Phys. Lett.
209
,
29
(
1993
).
64.
J.
Harrington
and
J. C.
Weisshaar
,
J. Chem. Phys.
97
,
2809
(
1992
).
65.
E. D.
Poliakoff
,
M.-H.
Ho
,
G. E.
Leroi
, and
M. G.
White
,
J. Chem. Phys.
84
,
4779
(
1986
).
66.
E. D.
Poliakoff
,
M.-H.
Ho
,
M. G.
White
, and
G. E.
Leroi
,
Chem. Phys. Lett.
130
,
91
(
1986
).
67.
L. A.
Kelly
,
L.
Duffy
,
B.
Space
,
E. D.
Poliakoff
,
M. G.
White
,
S. H.
Southworth
, and
P.
Roy
,
J. Chem. Phys.
90
,
1544
(
1989
).
68.
S.
Kakar
,
H. C.
Choi
, and
E. D.
Poliakoff
,
Chem. Phys. Lett.
190
,
489
(
1992
).
69.
S.
Kakar
,
H. C.
Choi
, and
E. D.
Poliakoff
,
J. Chem. Phys.
97
,
4690
(
1992
).
70.
S.
Kakar
,
E. D.
Poliakoff
, and
R. A.
Rosenberg
,
J. Chem. Phys.
96
,
23
(
1992
).
71.
B. C.
Craft
,
M.
Feldman
,
E.
Morikawa
,
E. D.
Poliakoff
,
V.
Saile
,
J. D.
Scott
, and
R. L.
Stockbauer
,
Rev. Sci. Instrum.
63
,
1561
(
1992
).
72.
E.
Morikawa
,
J. D.
Scott
,
E. D.
Poliakoff
,
R. L.
Stockbauer
, and
V.
Saile
,
Rev. Sci. Instrum.
63
,
1300
(
1992
).
73.
D. H.
Levy
,
Ann. Rev. Phys. Chem.
31
,
197
(
1980
).
74.
K. Wang and V. McKoy, in Highly Resolved Laser Photoionization and Photoelectron Studies, edited by I. Powis (Wiley, New York, 1995).
75.
A. R. Edmonds, Angular Momentum in Quantum Mechanics (Princeton University, Princeton, 1974).
76.
M.
Braunstein
,
V.
McKoy
, and
S. N.
Dixit
,
J. Chem. Phys.
96
,
5726
(
1992
).
77.
R. R.
Lucchese
,
K.
Takatsuka
, and
V.
McKoy
,
Phys. Rep.
131
,
147
(
1986
).
78.
R. R.
Lucchese
,
G.
Raseev
, and
V.
McKoy
,
Phys. Rev. A
25
,
2572
(
1982
).
79.
H. C. Choi, Ph.D. thesis, Louisiana State University.
80.
G. Herzberg, in Molecular Spectra and Molecular Structure, I. Spectra of Diatomic Molecules (Krieger, Malabar, FL, 1989).
81.
E. D.
Poliakoff
,
J. L.
Dehmer
,
D.
Dill
,
A. C.
Parr
,
K. H.
Jackson
, and
R. N.
Zare
,
Phys. Rev. Lett.
46
,
907
(
1981
).
82.
J. A. Guest, K. H. Jackson, and R. N. Zare, Phys. Rev. A28, 2217 (1983).
83.
J. A.
Guest
,
M. A.
O’Halloran
, and
R. N.
Zare
,
J. Chem. Phys.
81
,
2689
(
1984
).
84.
R.
Das
,
C.
Wu
,
A. G.
Mihill
,
E. D.
Poliakoff
,
K.
Wang
, and
V.
McKoy
,
J. Chem. Phys.
101
,
5402
(
1994
).
85.
R.
Das
,
C.
Wu
,
A. G.
Mihill
,
E. D.
Poliakoff
,
K.
Wang
, and
V.
McKoy
,
J. Phys. Chem.
99
,
1741
(
1995
).
86.
E. P.
Muntz
,
Phys. Fluids
5
,
80
(
1962
).
87.
B. M.
DeKoven
,
D. H.
Levy
,
H. H.
Harris
,
B. R.
Zegarski
, and
T. A.
Miller
,
J. Chem. Phys.
74
,
5659
(
1981
).
88.
J.
Kreile
,
A.
Schweig
, and
W.
Thiel
,
Chem. Phys. Lett.
108
,
259
(
1984
).
89.
A.
Hamnett
,
W.
Stoll
, and
C. E.
Brion
,
J. Electron. Spectrosc.
8
,
367
(
1976
);
E. W.
Plummer
,
T.
Gustafsson
,
W.
Gudat
, and
D. E.
Eastman
,
Phys. Rev. A
15
,
2339
(
1977
).
90.
J.
Davenport
,
Phys. Rev. Lett.
36
,
945
(
1976
).
91.
D.
Dill
and
J. L.
Dehmer
,
J. Chem. Phys.
61
,
692
(
1974
);
S.
Wallace
,
D.
Dill
, and
J. L.
Dehmer
,
J. Phys. B
12
,
L417
(
1979
);
J. L.
Dehmer
,
D.
Dill
, and
S.
Wallace
,
Phys. Rev. Lett.
43
,
1005
(
1979
).
92.
E. D.
Poliakoff
,
B.
Space
,
L. A.
Kelly
,
L.
Duffy
,
M. G.
White
,
S. H.
Southworth
, and
P.
Roy
,
J. Chem. Phys.
89
,
4048
(
1988
).
93.
E. D.
Poliakoff
,
B.
Space
,
L. A.
Kelly
,
L.
Duffy
,
M. G.
White
,
S. H.
Southworth
, and
P.
Roy
,
Chem. Phys.
129
,
65
(
1989
).
94.
R. M. Rao, J. Wu, and E. D. Poliakoff (to be published).
95.
I.
Tokue
,
A.
Masuda
,
H.
Kume
, and
Y.
Ito
,
Chem. Phys.
158
,
161
(
1991
).
96.
S. P.
Hernandez
,
P. J.
Dagdigian
, and
J. P.
Doering
,
Chem. Phys. Lett.
91
,
409
(
1982
);
S. P.
Hernandez
,
P. J.
Dagdigian
, and
J. P.
Doering
,
J. Chem. Phys.
77
,
6021
(
1982
);
P. J.
Dagdigian
and
J. P.
Doering
,
78
,
1846
(
1983
).,
J. Chem. Phys.
97.
H.
Helvajian
,
B. M.
DeKoven
, and
A. P.
Baronavski
,
Chem. Phys.
90
,
175
(
1984
).
98.
P. W.
Zetner
,
M.
Darrach
,
P.
Hammond
,
W. B.
Weterveld
,
R. L.
McConkey
, and
J. W.
McConkey
,
Chem. Phys.
124
,
453
(
1988
).
99.
A.
Nakajima
,
T.
Nagata
,
T.
Kondow
, and
K.
Kuchitsu
,
Chem. Phys. Lett.
151
,
511
(
1988
).
100.
See, for example, Atomic and Molecular Beam Methods, edited by G. Scoles (Oxford University, New York, 1988), Vol. 1, and references therein.
101.
P. C.
Engelking
,
Chem. Rev.
91
,
399
(
1991
).
102.
E. D. Poliakoff, R. M. Rao, A. G. Mihill, K. Wang, and V. McKoy (to be published).
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