Measurements of negative‐ion mobilities in pure O2 were made as a function of gas pressure (2–700 Torr), gas temperature (77.4° to 373°K), and electric field. Values of E/N, electric field over gas density, ranged from 6×10−19 to 6×10−17 V·cm2 so that the ions were in thermal equilibrium with the gas. The ion mobility times gas density μN is independent of density for 195°K and above. Values of μN for this ion, O2, are 5.7×1019, 6.5×1019, 6.8×1019 V−1·sec−1·cm−1 for temperatures of 195°, 300°, and 373°K, respectively. The density dependence of the measured mobilities at 77.4° and 87.6°K is consistent with an equilibrium between the concentrations of O2 and O4 ions. The low‐density data yield values of μN for the O2 ion of 4.7×1019 and 4.9×1019 V−1·sec−1·cm−1 at 77.4° and 87.6°K. The μN value of O4 ions is 2.6±0.5×1019 V−1·sec−1·cm−1 at both temperatures. Correlation with models for the internal motion of O4 leads to an estimated dissociation energy of 0.06±0.02 eV.

1.
A.
Doehring
,
Z. Naturforsch.
7a
,
253
(
1952
).
2.
E. W.
McDaniel
and
H. R.
Crane
,
Rev. Sci. Instr.
28
,
684
(
1957
).
3.
D. S.
Burch
and
R.
Geballe
,
Phys. Rev.
106
,
183
(
1957
).
4.
L. M.
Chanin
,
A. V.
Phelps
, and
M. A.
Biondi
,
Phys. Rev.
128
,
219
(
1962
).
5.
H.
Eiber
,
Z. Angew. Phys.
15
,
103
,
461
(
1963
); these results confirm earlier proposals based on higher E/N data in Ref. 4.
6.
J. A.
Rees
,
Australian J. Phys.
18
,
41
(
1965
).
7.
E. C.
Beaty
,
L. M.
Branscomb
, and
P. L.
Patterson
,
Bull. Am. Phys. Soc.
9
,
535
(
1964
);
and E. C. Beaty (private communication).
8.
J. L.
Pack
and
A. V.
Phelps
,
Phys. Rev.
121
,
798
(
1961
).
9.
R. J.
Munson
and
A. M.
Tyndall
,
Proc. Roy. Soc. (London)
A172
,
28
(
1939
).
For recent reviews see E. W. McDaniel, Collision Phenomena in Ionized Gases (John Wiley & Sons, Inc., New York, 1964),
or J. B. Hasted, Physics of Atomic Collisions (Butterworth Inc., Washington, D.C., 1964).
10.
J. J.
Lowke
,
Australian J. Phys.
15
,
39
(
1962
).
11.
A. V.
Phelps
and
J. L.
Pack
,
Phys. Rev. Letters
6
,
111
(
1961
)
and
J. L.
Pack
and
A. V.
Phelps
,
Bull. Am. Phys. Soc.
7
,
131
(
1962
).
A summary of this and related work is given in A. V. Phelps and J. L. Pack, Symp. Combust. 10th, Cambridge, England, 569, 1965.
12.
H.
Eyring
,
J. O.
Hirschfelder
, and
H. S.
Taylor
,
J. Chem. Phys.
4
,
479
(
1936
).
13.
R. N.
Varney
,
J. Chem. Phys.
31
,
1314
(
1959
);
R. N.
Varney
,
33
,
1709
(
1960
).,
J. Chem. Phys.
14.
J. L.
Pack
and
A. V.
Phelps
,
Bull. Am. Phys. Soc.
7
,
636
(
1962
).
15.
J.
Yang
and
D. C.
Conway
,
J. Chem. Phys.
40
,
1729
(
1964
).
16.
G. Herzberg, Infrared and Raman Spectra (D. Van Nostrand Company, Inc., New York, 1945), pp. 508–511.
17.
See, however,
D. C.
Conway
,
J. Chem. Phys.
36
,
2549
(
1962
).
18.
J. L.
Magee
and
F.
Funabashi
,
Radiation Res.
10
,
622
(
1959
).
19.
G. N.
Lewis
,
J. Am. Chem. Soc.
46
,
2027
(
1924
).
20.
See, for example, L. Pauling, The Nature of the Chemical Bond (Cornell University Press, Ithaca, New York, 1948), 2nd ed.
21.
It should be noted that in the experiments of Refs. 5 and 7 a corona discharge was used as an ion source so that several ions were observed simultaneously at some E/N. The source used in Ref. 6 was a hot filament in the presence of a relatively large electric field. All of those sources appear to produce O,O2, and O3ions in relative concentrations which depend upon gas density and electric‐field strength.5 The O2ions have the lowest mobility.5–7 The photoelectric source and unifromly low E/N values used in the present experiments and the low E/N region of the data of CPB are consistent with the production of a single ion, O2 at temperatures above 195 °K.
22.
A.
Dalgarno
,
Phil. Trans. Roy. Soc. (London)
A250
,
426
(
1958
).
23.
Measurements of the charge‐transfer cross section for O2 in O2 and for ion energies above 70 eV have been reported by
T. L.
Bailey
and
P.
Mahadevan
,
Bull. Am. Phys. Soc.
Ser. II
6
,
387
(
1961
).
24.
D. G.
Hummer
,
R. F.
Stebbings
,
W. L.
Fite
, and
L. M.
Branscomb
,
Phys. Rev.
119
,
668
(
1960
)
and
Yu. F.
Bydin
,
Zh. Eksperim. i Teor. Fiz.
46
,
1612
(
1964
)
[English transl.:
Yu. F.
Bydin
,
Soviet Phys.‐JETP
19
,
109
(
1964
)].
25.
T. Holstein (private communication).
26.
M. H.
Johnson
,
Phys. Rev.
80
,
101
(
1950
);
S.
Geltman
,
Phys. Rev.
94
,
1072
(
1954
); ,
Phys. Rev.
and
A. M.
Arthurs
and
A.
Dalgarno
,
Proc. Roy. Soc. (London)
A256
,
552
(
1960
).
27.
E. A.
Mason
and
H. W.
Schamp
, Jr.
,
Ann. Phys. N.Y.
4
,
233
(
1958
).
28.
M. L.
Mentzoni
,
Phys. Rev.
134
,
A80
(
1964
).
29.
H.
Margenau
,
Phil. Sci.
8
,
603
(
1941
).
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