Using a high‐resolution crossed‐beam apparatus, we have measured the integral cross section for the title reactions in the collision energy range from 0.025 to about 2 eV. Structure in the energy dependence of the cross section has been observed for both reactions. However, features for H2 and D2 appear at different collision energies. This has been attributed to the successive opening, as collision energy increases, of new adiabatic reactive channels via different vibronic states of the intermediate charge transfer complex N2+X2+(v) (X=H,D). Calculations of model potential energy surfaces show that the reactants’ surface does not cross the vibronic ground state. Therefore reactions proceed only via excited vibronic states resulting, in agreement with data from previous experiments, in vibrationally excited products.

1.
R. H.
Schultz
and
P. B.
Armentrout
,
J. Chem. Phys.
96
,
1036
(
1992
).
2.
G.
Gioumousis
and
D. P.
Stevenson
,
J. Chem. Phys.
29
,
294
(
1958
).
3.
(a)
V.
Aquilanti
,
A.
Galli
,
A.
Giardini-Guidoni
, and
G. G.
Volpi
,
J. Chem. Phys.
43
,
1969
(
1965
);
(b)
F. C.
Fehsenfeld
,
A. L.
Schmeltekopf
, and
E. E.
Ferguson
,
J. Chem. Phys.
46
,
2802
(
1967
); ,
J. Chem. Phys.
(c)
M. T.
Bowers
,
D. D.
Elleman
, and
J.
King
,Jr.
,
J. Chem. Phys.
50
,
1840
(
1968
); ,
J. Chem. Phys.
(d)
K. R.
Ryan
,
J. Chem. Phys.
61
,
1559
(
1974
); ,
J. Chem. Phys.
(e)
J. K.
Kim
,
L. P.
Theard
, and
W. T.
Huntress
,Jr.
,
J. Chem. Phys.
62
,
45
(
1975
); ,
J. Chem. Phys.
(f)
M.
Tichy
,
A. B.
Rakshit
,
D. G.
Lister
,
N. D.
Twiddy
,
N. G.
Adams
, and
D.
Smith
,
Int. J. Mass Spectrom. Ion Phys.
29
,
231
(
1979
).
4.
M. T.
Bowers
and
D. D.
Elleman
,
J. Chem. Phys.
51
,
4606
(
1969
).
5.
B. R.
Rowe
,
J. B.
Marquette
, and
C.
Rebrion
,
J. Chem. Soc. Faraday Trans. 2
85
,
1631
(
1989
).
6.
L. K.
Randeniya
and
M. A.
Smith
,
J. Chem. Phys.
94
,
351
(
1991
).
7.
W. R.
Gentry
,
E. A.
Gislason
,
B. H.
Mahan
, and
Chi-Wing
Tsao
,
J. Chem. Phys.
49
,
3058
(
1968
).
8.
P. M.
Hierl
,
L. W.
Strattan
, and
J. R.
Wyatt
,
Int. J. Mass Spectrom. Ion Phys.
10
,
385
(
1973
).
9.
B. R.
Turner
,
M. A.
Fineman
, and
R. F.
Stebbings
,
J. Chem. Phys.
42
,
4088
(
1965
).
10.
K.
Lacmann
and
A.
Henglein
,
Ber. Bunsenges Phys. Chem.
69
,
279
(
1965
).
11.
Z.
Herman
,
J.
Kerstetter
,
T.
Rose
, and
R.
Wolfgang
,
J. Chem. Phys.
46
,
2844
(
1967
).
12.
S. L.
Anderson
,
T.
Turner
,
B. H.
Mahan
, and
Y. T.
Lee
,
J. Chem. Phys.
77
,
1842
(
1982
).
13.
I.
Koyano
,
K.
Tanaka
,
T.
Kato
, and
S.
Suzuki
,
Faraday Discuss. Chem. Soc.
84
,
14
(
1987
).
14.
G.
Henri
,
M.
Lavollée
,
O.
Dutuit
,
J. B.
Ozenne
,
P. M.
Guyon
, and
E. A.
Gislason
,
J. Chem. Phys.
88
,
6381
(
1988
).
15.
P.
Tosi
,
F.
Eccher
,
D.
Bassi
,
F.
Pirani
,
D.
Cappelletti
, and
V.
Aquilanti
,
Phys. Rev. Lett.
67
,
1254
(
1991
).
16.
P. Tosi, O. Dmitrijev, Y. Soldo, D. Bassi, D. Cappelletti, F. Pirani, and V. Aquilanti (to be published).
17.
P.
Tosi
,
G.
Fontana
,
S.
Longano
, and
D.
Bassi
,
Int. J. Mass Spectrom. Ion Proc.
93
,
95
(
1989
).
18.
P.
Tosi
,
F.
Boldo
,
F.
Eccher
,
M.
Filippi
, and
D.
Bassi
,
Chem. Phys. Lett.
164
,
471
(
1989
).
19.
D.
Gerlich
,
Adv. Chem. Phys.
82
,
1
(
1992
).
20.
T. F.
Moran
and
L.
Friedman
,
J. Chem. Phys.
42
,
2391
(
1965
).
21.
M.
Schwarzer
,
A.
Hansel
,
W.
Freysinger
,
N.
Oberhofer
,
W.
Lindinger
, and
E. E.
Ferguson
,
J. Chem. Phys.
95
,
7344
(
1991
).
22.
D. R. Miller, in Atomic and Molecular Beam Methods, edited by G. Scoles (Oxford University, New York, 1988), Vol. 1, p. 16.
23.
A. Münster, Statistical Thermodynamics (Springer, Berlin, 1969), Vol. 1, p. 430.
24.
K. M.
Ervin
and
P. B.
Armentrout
,
J. Chem. Phys.
83
,
166
(
1985
).
25.
(a)
P. J.
Chantry
,
J. Chem. Phys.
55
,
2746
(
1971
);
(b)
C.
Lifshitz
,
R. L. C.
Wu
,
T. O.
Tiernan
, and
D. T.
Terwillger
,
J. Chem. Phys.
68
,
274
(
1978
).,
J. Chem. Phys.
26.
N.
Aristov
and
P. B.
Armentrout
,
J. Am. Chem. Soc.
108
,
1806
(
1986
).
27.
During the course of this work, new measurements of the rate constants in the collision energy range from thermal up to 0.2 eV were performed in a flow-drift tube by W. Freysinger at the Institute fur Ionenphysik, University of Innsbruck, Austria, who kindly provided us with his results.
28.
E.
Bauer
,
E. R.
Fisher
, and
F. R.
Gilmore
,
J. Chem. Phys.
51
,
4173
(
1969
).
29.
(a)
G. H.
Dunn
,
J. Chem. Phys.
44
,
1592
(
1966
);
(b)
J. L.
Gardner
and
J. A. R.
Samson
,
J. Electron. Spectrosc. Relat. Phenom.
13
,
7
(
1978
).
30.
(a)
R.
Cambi
,
D.
Cappelletti
,
G.
Liuti
, and
F.
Pirani
,
J. Chem. Phys.
95
,
1852
(
1991
);
(b)
D.
Cappelletti
,
G.
Liuti
, and
F.
Pirani
,
Chem. Phys. Lett.
183
,
297
(
1991
).
31.
H.
Villinger
,
J. H.
Futrell
,
A.
Saxer
,
R.
Richter
, and
W.
Lindinger
,
J. Chem. Phys.
80
,
2543
(
1984
).
32.
A. A. Radzig and B. M. Smimov, Reference Data on Atoms, Molecules, and Ions (Springer, Berlin, 1985).
This content is only available via PDF.
You do not currently have access to this content.