Linewidths, unimolecular dissociation rates and product state distributions (PSDs) have been measured for single rovibratational states of the ν1=5–7 levels of gas-phase trans-nitrous acid (HONO) by double-resonance overtone photofragment spectroscopy (DROPS). The linewidth measurements, together with the unimolecular dissociation rates in 1, suggest that the intramolecular dynamics are not statistical but rather depend sensitively upon specific intramolecular couplings and the vibrational character of the initial state. Comparison with calculated rate constants from statistical unimolecular rate theory reveals that intramolecular vibrational energy redistribution (IVR) is the rate determining step in the dissociation of HONO subsequent to vibrational overtone excitation. Despite this, we find the measured product state distributions to be close to the predictions of statistical theory. We explain these observations in terms of a simple tier model incorporating hierarchical IVR. The experimental findings underscore the importance of the preparation technique, and hence the nature of the initially excited state, in determining the subsequent intramolecular dynamics.

1.
A.
Callegari
and
T. R.
Rizzo
,
Chem. Soc. Rev.
30
,
214
(
2001
).
2.
C. B.
Moore
and
I. W. M.
Smith
,
J. Phys. Chem.
100
,
12848
(
1996
).
3.
V. A.
Mandelshtam
and
H. S.
Taylor
,
J. Chem. Phys.
103
,
2903
(
1995
).
4.
V. A.
Mandelshtam
and
H. S.
Taylor
,
Phys. Rev. Lett.
78
,
3274
(
1997
).
5.
R. Prosmiti, J. Tennyson, and D. C. Clary, in CCP 6, edited by R. Prosmiti, J. Tennyson, and D. C. Clary (CCP6, Daresbury, 1998).
6.
S.
Skokov
,
K. A.
Peterson
, and
J. M.
Bowman
,
J. Chem. Phys.
109
,
2662
(
1998
).
7.
S.
Skokov
,
J. M.
Bowman
, and
V. A.
Mandelshtam
,
PCCP
1
,
1279
(
1999
).
8.
J.
Hauschildt
,
J.
Weiss
,
C.
Beck
et al.,
Chem. Phys. Lett.
300
,
5
(
1999
).
9.
C.
Stock
,
X. N.
Li
,
H. M.
Keller
et al.,
J. Chem. Phys.
106
,
5333
(
1997
).
10.
R.
Schinke
,
C.
Beck
,
S. Y.
Grebenshchikov
, and
H.-M.
Keller
,
Ber. Bunsenges. Phys. Chem.
102
,
593
(
1998
).
11.
R.
Schinke
,
H.-M.
Keller
,
H.
Flöthmann
et al.,
Adv. Chem. Phys.
101
,
745
(
1997
).
12.
R. Schinke, Photodissociation Dynamics (Cambridge University Press, Cambridge, 1993).
13.
B.
Kirmse
,
B.
Abel
,
D.
Schwarzer
et al.,
J. Phys. Chem.
104
,
10398
(
2000
).
14.
J.
Troe
,
Adv. Chem. Phys.
101
,
819
(
1997
).
15.
M.
Quack
and
J.
Troe
,
Ber. Bunsenges. Phys. Chem.
78
,
240
(
1974
).
16.
T. Baer and W. L. Hase, Unimolecular Reaction Dynamics: Theory and Experiments (Oxford University Press, New York, Oxford, 1996).
17.
D. M.
Wardlaw
and
R. A.
Marcus
,
Chem. Phys. Lett.
110
,
230
(
1984
).
18.
D. M.
Wardlaw
and
R. A.
Marcus
,
J. Chem. Phys.
83
,
3462
(
1985
).
19.
D. M.
Wardlaw
and
R. A.
Marcus
,
J. Phys. Chem.
90
,
5383
(
1986
).
20.
X.
Luo
,
P. T.
Rieger
,
D. S.
Perry
, and
T. R.
Rizzo
,
J. Chem. Phys.
89
,
4448
(
1988
).
21.
X.
Luo
and
T. R.
Rizzo
,
J. Chem. Phys.
94
,
889
(
1991
).
22.
P. R.
Fleming
,
M. Y.
Li
, and
T. R.
Rizzo
,
J. Chem. Phys.
94
,
2425
(
1991
).
23.
M. R.
Wedlock
,
R.
Jost
, and
T. R.
Rizzo
,
J. Chem. Phys.
107
,
10344
(
1997
).
24.
S.
Reid
and
H.
Reisler
,
Annu. Rev. Phys. Chem.
47
,
495
(
1996
).
25.
I.
Bezel
,
D.
Stolyarov
, and
C.
Wittig
,
J. Phys. Chem.
103
,
10268
(
1999
).
26.
I.
Bezel
,
P.
Ionov
, and
C.
Wittig
,
J. Chem. Phys.
111
,
9267
(
1999
).
27.
S. I.
Ionov
,
G. A.
Bruckner
,
C.
Jaques
et al.,
J. Chem. Phys.
99
,
3420
(
1993
).
28.
S. I.
Ionov
,
H. F.
Davis
,
K.
Mikhaiylichenko
et al.,
J. Chem. Phys.
101
,
4809
(
1994
).
29.
P. I.
Ionov
,
I.
Bezel
,
S. I.
Ionov
, and
C.
Wittig
,
Chem. Phys. Lett.
272
,
257
(
1997
).
30.
X.
Luo
and
T. R.
Rizzo
,
J. Chem. Phys.
93
,
8620
(
1990
).
31.
B.
Kuhn
,
O. V.
Boyarkin
, and
T. R.
Rizzo
,
Ber. Bunsen-Ges. Phys. Chem. Chem. Phys.
101
,
339
(
1997
).
32.
W. H.
Polik
,
D. R.
Guyer
, and
C. B.
Moore
,
J. Chem. Phys.
92
,
3453
(
1990
).
33.
W. F.
Polik
,
D. R.
Guyer
,
W. H.
Miller
, and
C. B.
Moore
,
J. Chem. Phys.
92
,
3471
(
1990
).
34.
B.
Abel
,
H. H.
Hamann
, and
N.
Lange
,
Faraday Discuss.
102
,
147
(
1995
).
35.
U.
Robra
,
H.
Zacharias
, and
K. H.
Welge
,
Z. Phys. D: At., Mol. Clusters
16
,
175
(
1990
).
36.
J.
Miyawaki
,
K.
Yamanouchi
, and
S.
Tsuchiya
,
J. Chem. Phys.
101
,
4505
(
1994
).
37.
T. J.
Butenhoff
and
E. A.
Rohlfing
,
J. Chem. Phys.
98
,
5469
(
1993
).
38.
T. J.
Butenhoff
and
E. A.
Rohlfing
,
J. Chem. Phys.
98
,
5460
(
1993
).
39.
J. D.
Tobiason
,
J. R.
Dunlop
, and
E. A.
Rohlfing
,
J. Chem. Phys.
103
,
1448
(
1995
).
40.
D. W.
Neyer
,
X.
Luo
, and
P. L.
Houston
,
J. Chem. Phys.
98
,
5095
(
1993
).
41.
H. M.
Keller
,
M.
Stumpf
,
T.
Schroder
et al.,
J. Chem. Phys.
106
,
5359
(
1997
).
42.
S.
Reid
and
H.
Reisler
,
J. Phys. Chem.
100
,
474
(
1996
).
43.
Y. S.
Choi
and
C. B.
Moore
,
J. Chem. Phys.
97
,
1010
(
1992
).
44.
A.
Geers
,
J.
Kappert
,
F.
Temps
, and
J. W.
Wiebrecht
,
J. Chem. Phys.
101
,
3618
(
1994
).
45.
A.
Geers
,
J.
Kappert
,
F.
Temps
, and
J. W.
Wiebrecht
,
J. Chem. Phys.
101
,
3634
(
1994
).
46.
S.
Dertinger
,
A.
Geers
,
J.
Kappert
et al.,
Faraday Discuss. Chem. Soc.
102
,
31
(
1995
).
47.
B. R.
Foy
,
M. P.
Cassassa
,
J. C.
Stephenson
, and
J. S.
King
,
J. Chem. Phys.
90
,
7037
(
1989
).
48.
B. R.
Foy
,
M. P.
Casassa
,
J. C.
Stephenson
, and
J. S.
King
,
J. Chem. Phys.
92
,
2782
(
1990
).
49.
I. C.
Chen
,
W. H.
Greene
, and
C. B.
Moore
,
J. Chem. Phys.
89
,
314
(
1988
).
50.
W. H.
Greene
,
A. J.
Mahoney
,
Z. Q.
Ke
, and
C. B.
Moore
,
J. Chem. Phys.
94
,
1961
(
1991
).
51.
N. F.
Scherer
and
A. H.
Zewail
,
J. Chem. Phys.
87
,
97
(
1987
).
52.
A.
Callegari
,
J.
Rebstein
,
R.
Jost
, and
T. R.
Rizzo
,
J. Chem. Phys.
111
,
7359
(
1999
).
53.
R. J.
Barnes
,
G.
Dutton
, and
A.
Sinha
,
J. Phys. Chem. A
101
,
8374
(
1997
).
54.
G.
Dutton
,
R. J.
Barnes
, and
A.
Sinha
,
J. Chem. Phys.
111
,
4976
(
1999
).
55.
C. X. W.
Quian
,
M.
Noble
,
I.
Nadler
et al.,
J. Chem. Phys.
83
,
5573
(
1985
).
56.
X.
Luo
and
T. R.
Rizzo
,
J. Chem. Phys.
96
,
5129
(
1992
).
57.
D. Fulle, PhD thesis, University Göttingen, 1992.
58.
F.
Reiche
,
B.
Abel
,
R. D.
Beck
, and
T. R.
Rizzo
,
J. Chem. Phys.
112
,
8885
(
2000
).
59.
J.
Murto
,
M.
Rasanen
,
A.
Aspiala
, and
T.
Lotta
,
J. Mol. Struct.
122
,
213
(
1985
).
60.
J. A.
Darsey
and
D. L.
Thompson
,
J. Chem. Phys.
91
,
3168
(
1987
).
61.
S.
Nakamura
,
M.
Takahasi
,
M.
Okazaki
, and
K.
Morokuma
,
J. Am. Chem. Soc.
109
,
142
(
1987
).
62.
J. M.
Coffin
and
P.
Pulay
,
J. Phys. Chem.
95
,
118
(
1991
).
63.
S. M.
Holland
,
R. J.
Stickland
,
M. N. R.
Ashfold
et al.,
Chem. Soc. Faraday Trans.
87
,
3461
(
1991
).
64.
R.
Vasudev
,
R. N.
Zare
, and
R. N.
Dixon
,
J. Chem. Phys.
80
,
4863
(
1984
).
65.
R.
Vasudev
and
S. W.
Novicki
,
Chem. Phys.
226
,
201
(
1998
).
66.
R. N.
Dixon
and
H.
Rieley
,
J. Chem. Phys.
91
,
2308
(
1989
).
67.
J. R.
Huber
and
R.
Schinke
,
J. Phys. Chem.
97
,
3463
(
1993
).
68.
R.
Cotting
and
J. R.
Huber
,
J. Chem. Phys.
104
,
6208
(
1996
).
69.
J. M.
Guilmot
,
M.
Carleer
,
M.
Godefroid
, and
M.
Herman
,
J. Mol. Spectrosc.
143
,
81
(
1990
).
70.
J. M.
Guilmot
,
M.
Godefroid
, and
M.
Herman
,
J. Mol. Spectrosc.
160
,
387
(
1993
).
71.
J. M.
Guilmot
,
F.
Melen
, and
M.
Herman
,
J. Mol. Spectrosc.
160
,
401
(
1993
).
72.
G. H.
Dieke
and
H. M.
Crosswhite
,
JQSRT
2
,
97
(
1962
).
73.
W. L.
Dimpfl
and
J. L.
Kinsey
,
JQSRT
21
,
233
(
1979
).
74.
M.
Joyeux
,
D.
Sugny
,
M.
Lombardi
et al.,
J. Chem. Phys.
113
,
9610
(
2000
).
75.
J.
Hauschildt
,
J.
Weiss
, and
R.
Schinke
,
Z. Phys. Chem. (Munich)
5
,
609
(
2000
).
76.
A.
Callegari
,
J.
Rebstein
,
J. S.
Muenter
et al.,
J. Chem. Phys.
111
,
123
(
1999
).
77.
W. H.
Miller
,
R. H.
Hernandez
,
C. B.
Moore
, and
W. F.
Polik
,
J. Chem. Phys.
93
,
5657
(
1990
).
78.
R.
Hernandez
,
W. H.
Miller
,
C. B.
Moore
, and
W. F.
Polik
,
J. Chem. Phys.
99
,
950
(
1993
).
79.
M.
Gruebele
and
R.
Bigwood
,
Int. Rev. Phys. Chem.
17
,
91
(
1998
).
80.
R.
Jost
,
M.
Joyeux
,
S.
Skokov
, and
J. M.
Bowman
,
J. Chem. Phys.
111
,
6807
(
1999
).
81.
L.
Brouwer
,
C. J.
Cobos
,
J.
Troe
et al.,
J. Chem. Phys.
86
,
6171
(
1987
).
82.
J.
Troe
,
J. Chem. Phys.
79
,
6017
(
1983
).
83.
J.
Troe
,
J. Chem. Phys.
66
,
4758
(
1977
).
84.
J.
Troe
,
J. Chem. Phys.
66
,
4745
(
1977
).
85.
J.
Troe
,
J. Chem. Phys.
75
,
226
(
1981
).
86.
J.
Troe
,
J. Phys. Chem.
90
,
3485
(
1986
).
87.
J.
Troe
,
J. Chem. Phys.
87
,
2773
(
1987
).
88.
A. I.
Maergoiz
,
E. E.
Nikitin
, and
J.
Troe
,
J. Chem. Phys.
95
,
5117
(
1991
).
89.
A. I.
Maergoiz
,
E. E.
Nikitin
, and
J.
Troe
,
Z. Phys. Chem. (Munich)
172
,
129
(
1991
).
90.
A. I.
Maergoiz
,
E. E.
Nikitin
,
J.
Troe
, and
V. G.
Ushakov
,
J. Chem. Phys.
108
,
5265
(
1998
).
91.
L. B.
Harding
,
H.
Stark
,
J.
Troe
, and
V. G.
Ushakov
,
Phys. Chem. Chem. Phys.
1
,
63
(
1999
).
92.
A. J.
Dobbyn
,
M.
Stumpf
,
H. M.
Keller
et al.,
Faraday Discuss. Chem. Soc.
102
,
193
(
1995
).
93.
G. Herzberg, Molecular Spectra and Molecular Structure (Van Nostrand Reinhold, New York, London, 1945).
94.
C. M.
Deeley
,
I. M.
Mills
,
L. O.
Halonen
, and
J.
Kauppinen
,
Can. J. Phys.
63
,
962
(
1985
).
95.
S. W.
Novicki
and
R.
Vasudev
,
J. Chem. Phys.
95
,
7269
(
1991
).
96.
See EPAPS Document No. E-JCPSA6-116-002220 for a list of specific rate constants k(E,J) calculated by the SACM.
This document may be retrieved via the EPAPS homepage (http://www.aip.org/pubservs/epaps.html) or from ftp.aip.org in the directory /epaps/. See the EPAPS homepage for more information.
97.
D. J.
Nesbitt
and
R. W.
Field
,
J. Phys. Chem.
100
,
12735
(
1996
).
98.
M.
Quack
,
Annu. Rev. Phys. Chem.
41
,
839
(
1990
).
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