Translational energy thresholds have been measured for electron transfer reactions from various atomic negative ions to NO, NO2, SO2, CS2, Cl2, Br2, I2, and C2H2 using a tandem mass spectrometer. These thresholds, corrected where necessary for thermal broadening, were utilized with known thermodynamic data to calculate electron affinities for the molecules indicated. These results were also shown to be consistent with electron affinity limits established by observations of certain exothermic reactions of the molecular negative ions. The isotope distributions in the products from the reactions of monoisotopic Cl and Br with natural Cl2 and Br2, respectively, suggest that these reactions proceed via a linear X3 intermediate in which good ``mixing'' of the available energy occurs. The implications of this model with respect to the significance of the measured energy thresholds is discussed.

1.
B.
Moiseiwitsch
,
Adv. At. Mol. Phys.
1
,
61
(
1965
).
2.
R. S.
Berry
,
Chem. Rev.
69
,
533
(
1969
).
3.
F. M. Page and G. C. Goode, Negative Ions and the Magnetron (Wiley, New York, 1969).
4.
J. J.
DeCorpo
and
J. L.
Franklin
,
J. Chem. Phys.
54
,
1885
(
1971
).
5.
R. K. B.
Helbing
and
E. W.
Rothe
,
J. Chem. Phys.
51
,
1607
(
1969
).
6.
A. P. M.
Baede
,
A. M. C.
Moutinho
,
A. E.
deVries
, and
J.
Los
,
Chem. Phys. Lett.
3
,
530
(
1969
).
7.
K.
Lacmann
and
D. R.
Herschbach
,
Chem. Phys. Lett.
6
,
106
(
1970
).
8.
A. M. C.
Moutinho
,
A. P. M.
Baede
, and
J.
Los
,
Physica (Utr.)
51
,
432
(
1971
).
9.
S. J. Nalley, R. N. Compton, H. C. Schweinler, and P. W. Reinhardt, Rept. No. ORNL‐TM‐2620, “Collisional Ionization Between Cesium and Selected Molecules,” Oak Ridge National Laboratory, Oak Ridge, TN, April 1971.
10.
S. J.
Nalley
and
R. N.
Compton
,
Chem. Phys. Lett.
9
,
529
(
1971
).
11.
C.
Lifshitz
,
B. M.
Hughes
, and
T. O.
Tiernan
,
Chem. Phys. Lett.
7
,
469
(
1970
).
12.
T. O.
Tiernan
,
B. M.
Hughes
, and
C.
Lifshitz
,
J. Chem. Phys.
55
,
5692
(
1971
).
13.
W. A.
Chupka
,
J.
Berkowitz
, and
D.
Gutman
,
J. Chem. Phys.
55
,
2724
(
1971
).
14.
K.
Berkling
,
R.
Helbing
,
K.
Kramer
,
H.
Pauly
,
Ch.
Schlier
, and
P.
Toschek
,
Z. Phys.
166
,
406
(
1962
).
15.
Fr.
von Busch
,
H. J.
Strunck
, and
Ch.
Schlier
,
Z. Phys.
199
,
518
(
1967
).
16.
E. W.
Rothe
and
R. W.
Fenstermaker
,
J. Chem. Phys.
54
,
4520
(
1971
).
17.
P. J.
Chantry
,
J. Chem. Phys.
55
,
2746
(
1971
).
18.
J. H.
Futrell
and
C. D.
Miller
,
Rev. Sci. Instrum.
37
,
1521
(
1966
).
19.
B. M.
Hughes
and
T. O.
Tiernan
,
J. Chem. Phys.
55
,
3419
(
1971
).
20.
K. R. Spangenberg, Vacuum Tubes (McGraw‐Hill, New York, 1948), pp. 349 and 379.
21.
E. A. Soa, Jenaer Jahrbuch 1959/1 (Zeiss, Jena, 1959).
22.
J. A.
Simpson
,
Rev. Sci. Instrum.
32
,
1283
(
1961
).
23.
T. O.
Tiernan
and
R. E.
Marcotte
,
J. Chem. Phys.
53
,
2107
(
1970
).
24.
F. C. Fehsenfeld, A. L. Schmeltekopf, D. B. Dunkin, and E. E. Ferguson, ESSA Technical Report ERL +35‐AL3, U.S. Dept. of Commerce, Washington, DC, 1969.
25.
P.
Pechukas
and
J. C.
Light
,
J. Chem. Phys.
42
,
3281
(
1965
).
26.
D. G.
Truchlar
,
J. Chem. Phys.
51
,
4617
(
1969
).
27.
H. A.
Bethe
,
Rev. Mod. Phys.
9
,
69
(
1937
);
H. A.
Bethe
and
G.
Placzek
,
Phys. Rev.
51
,
450
(
1937
).
28.
J. A.
Rutherford
and
B. R.
Turner
,
J. Geophys. Res.
72
,
3795
(
1967
).
29.
T. L.
Bailey
and
P.
Mahadevan
,
J. Chem. Phys.
52
,
179
(
1970
).
30.
J. M.
Williams
and
W. H.
Hamill
,
J. Chem. Phys.
49
,
4467
(
1968
).
31.
J. A. D.
Stockdale
,
R. N.
Compton
,
G. S.
Hurst
, and
P. W.
Reinhardt
,
J. Chem. Phys.
50
,
2176
(
1969
).
32.
D.
Spence
and
G. J.
Schulz
,
Phys. Rev.
188
,
280
(
1969
).
33.
D.
Spence
and
G. J.
Schulz
,
Phys. Rev. A
3
,
1968
(
1971
).
34.
R.
Celotta
,
R.
Bennett
,
J.
Hall
,
M. W.
Siegel
, and
J.
Levine
,
Bull. Am. Phys. Soc.
15
,
1515
(
1970
).
In the thesis which describes these results (M. W. Siegel, Univ. Colorado, Boulder, thesis, 1970; Univ. Microfilms Order No. 70‐23754), a somewhat higher value of E.A. (NO) = 0.047±0.005 eV is cited, which is obtained after compensating for the rotational energy distributions in the states involved in the transition.
35.
J.
Berkowitz
,
W. A.
Chupka
, and
D.
Gutman
,
J. Chem. Phys.
55
,
2733
(
1971
).
36.
F. C.
Fehsenfeld
,
E. E.
Ferguson
, and
A. L.
Schmeltekopf
,
J. Chem. Phys.
45
,
7844
(
1966
).
37.
J. F.
Paulson
,
J. Chem. Phys.
52
,
959
(
1970
).
38.
S. J. Nally, R. N. Compton, H. C. Schweinler, and V. E. Anderson, J. Chem. Phys. (to be published).
39.
K.
Lacmann
and
D. R.
Herschbach
,
Chem. Phys. Lett.
6
,
106
(
1970
).
40.
R. S.
Berry
and
C. W.
Reimann
,
J. Chem. Phys.
38
,
1510
(
1963
).
41.
B. M. Hughes and T. O. Tiernan, Paper No. 15, 16th Annual Conference on Mass Spectrometry and Allied Topics, Pittsburgh, PA, May 1968.
42.
E. E.
Ferguson
,
F. C.
Fehsenfeld
, and
A. L.
Schmeltekopf
,
J. Chem. Phys.
47
,
3085
(
1967
).
43.
E. E. Ferguson, Advances in Electronics and Electron Physics, edited by L. Marton (Academic, New York, 1968), Vol. 24, p. 1.
44.
F. A.
Wolf
and
B. R.
Turner
,
J. Chem. Phys.
48
,
4226
(
1968
).
45.
T. O. Tiernan and B. M. Hughes, Paper No. 13, 16th Annual Conference on Mass Spectrometry and Allied Topics, Pittsburgh, PA, May 1968.
46.
D.
Vogt
,
Int. J. Mass Spectrom. Ion Phys.
3
,
81
(
1969
).
47.
D. B.
Dunkin
,
F. C.
Fehsenfeld
, and
E. E.
Ferguson
,
Chem. Phys. Lett.
15
,
257
(
1972
);
E. E. Ferguson (private communication).
48.
A. P. M.
Baede
,
Physica (Utr.)
59
,
541
(
1972
).
49.
K.
Lacmann
and
D. R.
Herschbach
,
Bull. Am. Phys. Soc.
16
,
213
(
1971
).
50.
C. B. Leffert, W. M. Jackson, and E. W. Rothe, J. Chem. Phys. (to be published);
E. W. Rothe (private communication).
51.
P.
Warneck
,
Chem. Phys. Lett.
3
,
532
(
1969
).
52.
K.
Kraus
,
W.
Muller‐Dusping
, and
H.
Neuert
,
Z. Naturforsch. A
16
,
1385
(
1961
).
53.
D.
Vogt
,
B.
Hauffe
, and
H.
Neuert
,
Z. Phys.
232
,
439
(
1970
).
54.
D.
Feldmann
,
Z. Naturforsch. A
25
,
621
(
1970
).
55.
G. Herzberg, Electronic Spectra of Polyatomic Molecules (Van Nostrand, New York, 1966).
56.
J. H. Futrell and T. O. Tiernan, in Ion‐Molecule Reactions, edited by J. H. Franklin (Plenum, New York, 1972), p. 477.
57.
G. C.
Pimentel
,
J. Chem. Phys.
19
,
446
(
1951
).
58.
C. D.
Cornwell
and
R. S.
Yamasaki
,
J. Chem. Phys.
27
,
1060
(
1957
).
59.
R. S.
Yamasaki
and
C. D.
Cornwell
,
J. Chem. Phys.
30
,
1265
(
1959
).
60.
W. B.
Person
,
G. R.
Anderson
,
J. N.
Fordemwalt
,
H.
Stammreich
, and
R.
Forneris
,
J. Chem. Phys.
35
,
908
(
1962
).
61.
J. A. D.
Stockdale
,
R. N.
Compton
, and
P. W.
Reinhardt
,
Int. J. Mass Spectrom. Ion Phys.
4
,
401
(
1970
).
62.
D. K.
Bohme
,
E.
Lee‐Ruff
, and
L. B.
Young
,
J. Am. Chem. Soc.
94
,
5153
(
1972
).
63.
J. L.
Franklin
,
J. G.
Dillard
,
H. M.
Rosenstock
,
J. T.
Herron
, and
K.
Draxl
,
Natl. Stand. Ref. Data Ser.
26
(
1969
).
This content is only available via PDF.
You do not currently have access to this content.