Photodissociation of HOBr is an important step in the reaction network of the depletion of ozone in stratosphere. Here, we report the first three-dimensional potential energy surfaces for the lowest three singlet states for HOBr, based on high level multi reference configuration interaction calculations. Quantum dynamics calculations are performed with a real wavepacket method, yielding not only absorption spectra but also internal state and angular distributions of the photodissociation fragments. Our results agree quantitatively with the measured total absorption cross sections of HOBr in the ultraviolet region and reproduce well the observed vibrationally cold and rotationally hot OH/OD fragments via photodissociation of HOBr/DOBr at 266 nm. In addition, we predict that the recoil anisotropy parameters for OH/OD are close to the limiting value of a parallel transition, suggesting a rapid dissociation process at 266 nm following an in-plane transition from the ground state (11A′) to the 21A′ state. This is consistent with the experimental conclusion derived from the measured rotational alignment. However, spin and electronic angular momenta need to be taken into account in the future to achieve a more quantitative agreement with experiment. Our work is expected to motivate further experimental investigations for this benchmark system.

[2]
R. N.
Dixon
,
D. W.
Hwang
,
X. F.
Yang
,
S.
Harich
,
J. J.
Lin
, and
X.
Yang
,
Science
285
,
1249
(
1999
).
[3]
Y.
Chang
,
Y.
Yu
,
H.
Wang
,
X.
Hu
,
Q.
Li
,
J.
Yang
,
S.
Su
,
Z.
He
,
Z.
Chen
,
L.
Che
,
X.
Wang
,
W.
Zhang
,
G.
Wu
,
D.
Xie
,
M. N. R.
Ashfold
,
K.
Yuan
, and
X.
Yang
,
Nat. Commun.
10
,
1250
(
2019
).
[4]
D.
Townsend
,
S. A.
Lahankar
,
S. K.
Lee
,
S. D.
Chambreau
,
A. G.
Suits
,
X.
Zhang
,
J.
Rheinecker
,
L. B.
Harding
, and
J. M.
Bowman
,
Science
306
,
1158
(
2004
).
[5]
W.
Chen
,
L.
Zhang
,
D.
Yuan
,
Y.
Chang
,
S.
Yu
,
S.
Wang
,
T.
Wang
,
B.
Jiang
,
K.
Yuan
,
X.
Yang
, and
X.
Wang
,
J. Phys. Chem. Lett.
10
,
4783
(
2019
).
[6]
S.
Han
,
X.
Zheng
,
S.
Ndengué
,
Y.
Song
,
R.
Dawes
,
D.
Xie
,
J.
Zhang
, and
H.
Guo
,
Sci. Adv.
5
,
eaau0582
(
2019
).
[7]
X.
Hu
,
L.
Zhou
, and
D.
Xie
,
WIREs. Comput. Mol. Sci.
8
,
e1350
(
2018
).
[8]
Z.
Lu
,
Y. C.
Chang
,
Q. Z.
Yin
,
C. Y.
Ng
, and
W. M.
Jackson
,
Science
346
,
61
(
2014
).
[9]
A. R.
Whitehill
,
C.
Xie
,
X.
Hu
,
D.
Xie
,
H.
Guo
, and
S.
Ono
,
Proc. Natl. Acad. Sci. USA
110
,
17697
(
2013
).
[10]
G. G.
Balint-Kurti
,
L.
Füsti-Molnár
, and
A.
Brown
,
Phys. Chem. Chem. Phys.
3
,
702
(
2001
).
[11]
N.
Shaw
,
A. J.
Bell
,
M. J.
Crawford
, and
J. G.
Frey
,
J. Chem. Soc., Faraday Trans.
90
,
817
(
1994
).
[12]
T.
Ingham
,
D.
Bauer
,
J.
Landgraf
, and
J. N.
Crowley
,
J. Phys. Chem. A
102
,
3293
(
1998
).
[13]
I.
Schwager
and
A.
Arkell
,
J. Am. Chem. Soc.
89
,
6006
(
1967
).
[14]
Y.
Koga
,
H.
Takeo
,
S.
Kondo
,
M.
Sugie
,
C.
Matsumura
,
G. A.
McRae
, and
E. A.
Cohen
,
J. Mol. Spectrosc.
138
,
467
(
1989
).
[15]
G. A.
McRae
and
E. A.
Cohen
,
J. Mol. Spectrosc.
139
,
369
(
1990
).
[16]
T.
Benter
,
C.
Feldmann
,
M.
Kirchner
,
M.
Schmidt
,
S.
Schmidt
, and
R. N.
Schindler
,
Ber. Bunsenges. Phys. Chem.
99
,
1144
(
1995
).
[17]
E. A.
Cohen
,
G. A.
McRae
,
T. L.
Tan
,
R. R.
Friedl
,
J. W. C.
Johns
, and
M.
Noel
,
J. Mol. Spectrosc.
173
,
55
(
1995
).
[18]
J. J.
Orlando
and
J. B.
Burkholder
,
J. Phys. Chem.
99
,
1143
(
1995
).
[19]
R. J.
Barnes
,
M.
Lock
,
J.
Coleman
, and
A.
Sinha
,
J. Phys. Chem.
100
,
453
(
1996
).
[20]
B.
Deters
,
J. P.
Burrows
,
S.
Himmelmann
, and
C.
Blindauer
,
Ann. Geophys. (in Germany)
14
,
468
(
1996
).
[21]
M.
Lock
,
R. J.
Barnes
, and
A.
Sinha
,
J. Phys. Chem.
100
,
7972
(
1996
).
[22]
O. V.
Rattigan
,
D. J.
Lary
,
R. L.
Jones
, and
R. A.
Cox
,
J. Geophys. Res.
101
,
23021
(
1996
).
[23]
T. J.
Lee
,
J. Phys. Chem.
99
,
15074
(
1995
).
[24]
P.
Palmieri
,
C.
Puzzarini
, and
R.
Tarroni
,
Chem. Phys. Lett.
256
,
409
(
1996
).
[25]
K. A.
Peterson
,
Spectrochim. Acta A
53
,
1051
(
1997
).
[26]
L.
Fsti-Molnár
,
P. G.
Szalay
, and
G. G.
Balint-Kurti
,
J. Chem. Phys.
110
,
8448
(
1999
).
[27]
T. J.
Lee
,
S.
Parthiban
, and
M.
Head-Gordon
,
Spectrochim. Acta A
55
,
561
(
1999
).
[28]
B. F.
Minaev
,
J. Phys. Chem. A
103
,
7294
(
1999
).
[29]
K. A.
Peterson
,
J. Chem. Phys.
113
,
4598
(
2000
).
[30]
A.
Brown
,
G. G.
Balint-Kurti
, and
L.
Füsti-Molnár
,
Phys. Chem. Chem. Phys.
3
,
3973
(
2001
).
[31]
J. S.
Francisco
,
M. R.
Hand
, and
I. H.
Williams
,
J. Phys. Chem.
100
,
9250
(
1996
).
[32]
H. J.
Werner
,
P. J.
Knowles
,
R.
Lindh
,
F. R.
Manby
,
M.
Schütz
,
P.
Celani
,
W.
Györffy
,
D.
Kats
,
T.
Korona
,
R.
Lindh
,
A.
Mitrushenkov
,
G.
Rauhut
,
K. R.
Shamasundar
,
T. B.
Adler
,
R. D.
Amos
,
S. J.
Bennie
,
A.
Bernhardsson
,
A.
Berning
,
D. L.
Cooper
,
M. J. O.
Deegan
,
A. J.
Dobbyn
,
F.
Eckert
,
E.
Goll
,
C.
Hampel
,
A.
Hesselmann
,
G.
Hetzer
,
T.
Hrenar
,
G.
Jansen
,
C.
Köppl
,
S. J. R.
Lee
,
Y.
Liu
,
A. W.
Lloyd
,
Q.
Ma
,
R. A.
Mata
,
A. J.
May
,
S. J.
McNicholas
,
W.
Meyer
,
T. F.
Miller
III
,
M. E.
Mura
,
A.
Nicklaß
,
D. P.
O’Neill
,
P.
Palmieri
,
D.
Peng
,
K.
Pflüger
,
R.
Pitzer
,
M.
Reiher
,
T.
Shiozaki
,
H.
Stoll
,
A. J.
Stone
,
R.
Tarroni
,
T.
Thorsteinsson
,
M.
Wang
, and
M.
Welborn
,
MOLPRO, version 2012.1, a Package of ab initio Programs
, (
2012
), see http://www.molpro.net.
[33]
P. J.
Knowles
and
H. J.
Werner
,
Chem. Phys. Lett.
145
,
514
(
1988
).
[34]
H. J.
Werner
,
B.
Follmeg
, and
M. H.
Alexander
,
J. Chem. Phys.
89
,
3139
(
1988
).
[35]
H. J.
Werner
and
P. J.
Knowles
,
J. Chem. Phys.
82
,
5053
(
1985
).
[36]
P. J.
Knowles
and
H. J.
Werner
,
Chem. Phys. Lett.
115
,
259
(
1985
).
[37]
S. R.
Langhoff
and
E. R.
Davidson
,
Int. J. Quant. Chem.
8
,
61
(
1974
).
[38]
R. A.
Kendall
,
T. H.
Dunning
, and
R. J.
Harrison
,
J. Chem. Phys.
96
,
6796
(
1992
).
[39]
B.
Jiang
,
J.
Li
, and
H.
Guo
,
Int. Rev. Phys. Chem.
35
,
479
(
2016
).
[41]
G. G.
Balint-Kurti
and
M.
Shapiro
,
Chem. Phys.
61
,
137
(
1981
).
[42]
G. G.
Balint-Kurti
,
Adv. Chem. Phys.
128
,
249
(
2004
).
[43]
G. G.
Balint-Kurti
,
Int. Rev. Phys. Chem.
27
,
507
(
2008
).
[44]
R.
Schinke
,
Photodissociation Dynamics
,
Cambridge
:
Cambridge University Press
, (
1993
).
[46]
R.
van Harrevelt
and
M. C.
van Hemert
,
J. Chem. Phys.
112
,
5787
(
2000
).
[47]
H.
Flothmann
,
C.
Beck
,
R.
Schinke
,
C.
Woywod
, and
W.
Domcke
,
J. Chem. Phys.
107
,
7296
(
1997
).
[48]
B.
Jiang
,
D.
Xie
, and
H.
Guo
,
J. Chem. Phys.
134
,
231103
(
2011
).
[49]
B.
Jiang
,
D.
Xie
, and
H.
Guo
,
J. Chem. Phys.
136
,
034302
(
2012
).
[50]
L.
Zhou
,
D.
Xie
,
Z.
Sun
, and
H.
Guo
,
J. Chem. Phys.
140
,
024310
(
2014
).
[51]
G. S. M.
Lin
,
L. S.
Zhou
, and
D. Q.
Xie
,
J. Phys. Chem. A
118
,
9220
(
2014
).
[52]
L.
Zhou
,
D.
Xie
, and
H.
Guo
,
J. Chem. Phys.
142
,
124317
(
2015
).
[53]
L.
Zhou
,
B.
Jiang
,
D.
Xie
, and
H.
Guo
,
J. Phys. Chem. A
117
,
6940
(
2013
).
[54]
E. J.
Heller
,
J. Chem. Phys.
68
,
2066
(
1978
).
[55]
G. G.
Balint-Kurti
and
M.
Shapiro
,
Photodissociation and Photoionization
,
K. P.
Lawley
Ed.,
New York
:
Wiley
,
403
(
1985
).
[56]
H.
Tal-Ezer
and
R.
Kosloff
,
J. Chem. Phys.
81
,
3967
(
1984
).
[57]
Y.
Huang
,
D. J.
Kouri
, and
D. K.
Hoffman
,
Chem. Phys. Lett.
225
,
37
(
1994
).
[58]
V. A.
Mandelshtam
and
H. S.
Taylor
,
J. Chem. Phys.
103
,
2903
(
1995
).
[59]
W.
Zhu
,
Y.
Huang
,
D. J.
Kouri
,
C.
Chandler
, and
D. K.
Hoffman
,
Chem. Phys. Lett.
217
,
73
(
1994
).
[60]
A. R.
Edmonds
,
Angular Momentum in Quantum Mechanics
,
2nd Edn
.,
Princeton
:
Princeton University Press
(
1960
).
[61]
G. G.
Balint-Kurti
,
R. N.
Dixon
, and
C. C.
Marston
,
J. Chem. Soc. Faraday Trans.
86
,
1741
(
1990
).
[62]
R.
Chen
and
H.
Guo
,
Comput. Phys. Commun.
119
,
19
(
1999
).
[63]
D. T.
Colbert
and
W. H.
Miller
,
J. Chem. Phys.
96
,
1982
(
1992
).
[64]
G. C.
Corey
and
D.
Lemoine
,
J. Chem. Phys.
97
,
4115
(
1992
).
[65]
A. R.
Offer
and
G. G.
Balintkurti
,
J. Chem. Phys.
101
,
10416
(
1994
).
[66]
S.
Nanbu
and
S.
Iwata
,
J. Phys. Chem.
96
,
2103
(
1992
).
[67]
[68]
M. D.
Morse
and
K. F.
Freed
,
J. Chem. Phys.
78
,
6045
(
1983
).
[69]
A. R.
Offer
and
G. G.
Balint-Kurti
,
J. Chem. Phys.
104
,
563
(
1996
).
[70]
A. R.
Offer
and
G. G.
Balint-Kurti
,
Chem. Phys. Lett.
247
,
173
(
1995
).
[71]
R. N.
Dixon
,
J. Chem. Phys.
85
,
1866
(
1986
).
This content is only available via PDF.
You do not currently have access to this content.