The quantum state resolved rotational angular momentum alignments of the OH products of the H+CO2 reaction have been determined for a range of states spanning those most populated by reaction at a collision energy of 2.5 eV. Surprisingly, for all quantum states studied, the angular momentum is shown to be aligned preferentially in the scattering plane, containing the reagent and product relative velocity vectors. The data suggest that out-of-plane HO–CO torsional forces play a significant role in dissociation of the HOCO intermediate. The polarization behavior mirrors observed in the isoelectronic H+N2O reaction [see the accompanying paper, J. Chem. Phys. 113, 3162 (2000)], and the data are compared with those obtained for that system, and with previous theoretical and experimental work on this important reaction.

1.
J. D.
Barnwell
,
J. G.
Loeser
, and
D. R.
Herschbach
,
J. Phys. Chem.
87
,
2781
(
1983
).
2.
D. A.
Case
and
D. R.
Herschbach
,
Mol. Phys.
30
,
1537
(
1975
).
3.
G. M.
McClelland
and
D. R.
Herschbach
,
J. Phys. Chem.
83
,
1445
(
1979
).
4.
S. K.
Kim
and
D. R.
Herschbach
,
Faraday Discuss. Chem. Soc.
84
,
159
(
1987
).
5.
M. Brouard and J. P. Simons, in Chemical Dynamics and Kinetics of Small Free Radicals, edited by K. Liu and A. L. Wagner (World Scientific, Singapore, 1995), Part II, p. 195.
6.
A. J.
Alexander
,
M.
Brouard
,
K. S.
Kalogerakis
, and
J. P.
Simons
,
Chem. Soc. Rev.
27
,
405
(
1998
).
7.
A. J.
Orr-Ewing
and
R. N.
Zare
,
Annu. Rev. Phys. Chem.
45
,
315
(
1994
).
8.
A. J. Orr-Ewing and R. N. Zare, in Chemical Dynamics and Kinetics of Small Free Radicals, edited by K. Liu and A. L. Wagner (World Scientific, Singapore, 1995), Part II, p. 936.
9.
A. J.
Alexander
and
R. N.
Zare
,
J. Chem. Educ.
75
,
1105
(
1998
).
10.
A. J.
Orr-Ewing
,
J. Chem. Soc., Faraday Trans.
92
,
881
(
1996
).
11.
N. E.
Shafer-Ray
,
A. J.
Orr-Ewing
, and
R. N.
Zare
,
J. Phys. Chem.
99
,
7591
(
1995
).
12.
F. J.
Aoiz
,
M.
Brouard
,
P. A.
Enriquez
,
R.
Sayos
,
J. Chem. Soc., Faraday Trans.
89
,
1427
(
1993
).
13.
F. J.
Aoiz
,
M.
Brouard
, and
P. A.
Enriquez
,
J. Chem. Phys.
105
,
4964
(
1996
).
14.
M. P.
de Miranda
and
D. C.
Clary
,
J. Chem. Phys.
106
,
4509
(
1997
).
15.
M. P.
de Miranda
,
F. J.
Aoiz
,
L.
Bañares
, and
V.
Sáez Rábanos
,
J. Chem. Phys.
111
,
5368
(
1999
).
16.
M.
Brouard
,
H. M.
Lambert
,
S. P.
Rayner
, and
J. P.
Simons
,
Mol. Phys.
89
,
403
(
1996
).
17.
M.
Brouard
,
D. W.
Hughes
,
K. S.
Kalogerakis
, and
J. P.
Simons
,
J. Phys. Chem. A
102
,
9559
(
1998
).
18.
M. Brouard, D. W. Hughes, K. S. Kalogerakis, and J. P. Simons, J. Chem. Phys. (to be published).
19.
K.
Kleinermanns
,
E.
Linnebach
, and
J.
Wolfrum
,
J. Phys. Chem.
89
,
2525
(
1985
).
20.
A.
Jacobs
,
H.-R.
Volpp
, and
J.
Wolfrum
,
Chem. Phys. Lett.
218
,
51
(
1994
).
21.
G.
Radhakrishnan
,
S.
Buelow
, and
C.
Wittig
,
J. Chem. Phys.
84
,
727
(
1986
).
22.
S.
Buelow
,
G.
Radhakrishnan
, and
C.
Wittig
,
J. Phys. Chem.
91
,
5409
(
1987
).
23.
(a)
J. K.
Rice
,
Y. C.
Chung
, and
A. P.
Baronavski
,
Chem. Phys. Lett.
167
,
151
(
1990
); (b)
J. K.
Rice
, and
A. P.
Baronavski
,
J. Chem. Phys.
94
,
1006
(
1991
).
24.
S. L.
Nickolaisen
,
H. E.
Cartland
, and
C.
Wittig
,
J. Chem. Phys.
96
,
4378
(
1992
).
25.
M.
Brouard
,
I.
Burak
,
S. D.
Gatenby
,
G. A. J.
Markillie
,
Chem. Phys. Lett.
287
,
682
(
1997
).
26.
M.
Brouard
,
I.
Burak
,
S. D.
Gatenby
,
D.
Hart
, and
D.
Minayev
,
J. Chem. Phys.
110
,
11335
(
1999
).
27.
M. Brouard, I. Burak, and S. D. Gatenby, Phys. Chem. Chem. Phys. (to be published).
28.
M.
Brouard
,
S. D.
Gatenby
,
D. M.
Joseph
, and
C.
Vallance
,
J. Chem. Phys.
113
,
3162
(
2000
), preceding paper.
29.
G. C.
Schatz
,
M. S.
Fitzcharles
, and
L. B.
Harding
,
Faraday Discuss. Chem. Soc.
84
,
359
(
1987
).
30.
K. S.
Bradley
and
G. C.
Schatz
,
J. Chem. Phys.
106
,
8464
(
1997
).
31.
S. L. Wilsey and C. Vallance (unpublished results).
32.
Z.
Xu
,
B.
Koplitz
, and
C.
Wittig
,
J. Chem. Phys.
87
,
1062
(
1987
).
33.
Z.
Xu
,
B.
Koplitz
, and
C.
Wittig
,
J. Phys. Chem.
92
,
5518
(
1988
).
34.
M. N. R.
Ashfold
,
S. G.
Clement
,
J. D.
Howe
, and
C. W.
Western
,
J. Chem. Soc., Faraday Trans.
89
,
1153
(
1993
).
35.
P. M.
Regan
,
S. R.
Langford
,
A. J.
Orr-Ewing
, and
M. N. R.
Ashfold
,
J. Chem. Phys.
110
,
281
(
1999
), and references therein.
36.
H. Okabe, in Photochemistry of Small Molecules (Wiley-Interscience, New York, 1978).
37.
G. H.
Dieke
and
H. M.
Crosswhite
,
J. Quant. Spectrosc. Radiat. Transf.
2
,
97
(
1962
).
38.
M. P.
Docker
,
Chem. Phys.
135
,
405
(
1989
).
39.
J. P.
Simons
,
Faraday Discuss.
113
,
1
(
1999
).
40.
K. S.
Bradley
,
P.
McCabe
,
G. C.
Schatz
, and
S. P.
Walch
,
J. Phys. Chem.
102
,
6696
(
1995
).
41.
U.
Meier
and
V.
Staemmler
,
J. Phys. Chem.
95
,
6111
(
1991
).
42.
K.-H.
Gericke
,
M.
Lock
,
R.
Fasold
, and
F. J.
Comes
,
J. Chem. Phys.
96
,
422
(
1992
).
43.
K.-H.
Gericke
,
R.
Theinl
, and
F. J.
Comes
,
J. Chem. Phys.
92
,
6548
(
1990
).
44.
K.-H.
Gericke
,
T.
Haas
,
M.
Lock
,
R.
Theinl
, and
F. J.
Comes
,
J. Phys. Chem.
95
,
6104
(
1991
).
45.
N. F.
Scherer
,
C.
Sipes
,
R. B.
Bernstein
, and
A. H.
Zewail
,
J. Chem. Phys.
92
,
5239
(
1990
).
46.
H. L.
Kim
,
M. A.
Wickramaaratchi
,
X.
Zheng
, and
G. E.
Hall
,
J. Chem. Phys.
101
,
2033
(
1994
).
This content is only available via PDF.
You do not currently have access to this content.