The photochemistry of HOSO in the near- and deep-UV spectral range has been studied in the gas phase using the multireference configuration interaction MRCI+Q/aug-cc-pV(T+d)Z level of theory. HOSO is found to be a nonplanar radical in its ground electronic state with a torsion angle calculated to be 49.7°. The lowest three doublet electronic states are characterized by a large transition dipole moment and are implicated in the photodissociation of HOSO in the gas phase to generate SO and OH as products. Sulfur dioxide and hydrogen products may also result after UV absorption to reach the first excited state, and this channel competes with the production of OH and SO.

1.
S. T.
Ota
and
G. L.
Richmond
,
J. Am. Chem. Soc.
134
(
24
),
9967
9977
(
2012
).
2.
S.
Hattori
,
J. A.
Schmidt
,
M. S.
Johnson
,
S. O.
Danielache
,
A.
Yamada
,
Y.
Ueno
, and
N.
Yoshida
,
Proc. Natl. Acad. Sci. U. S. A.
110
(
44
),
17656
17661
(
2013
).
3.
M.
Sipila
,
T.
Brndt
,
T.
Petaja
,
D.
Brus
,
J.
Vanhanen
,
F.
Stratmann
,
J.
Patokoski
,
R. L.
Mauldin
 III
,
A. P.
Hyvarinen
,
H.
Lihavainen
, and
M.
Kulmala
,
Science
327
,
1243
1246
(
2010
).
4.
B. J.
Finlayson-Pitts
and
J. N.
Pitts
, Jr.
,
Chemistry of the Upper and Lower Atmosphere: Theory, Experiments and Applications
(
Academic Press
,
San Diego, CA
,
2000
), p.
969
.
5.
H.
Tachikawa
,
J. Phys. Chem. A
115
,
9091
9096
(
2011
).
6.
J.
Zhong
,
C.
Zhu
,
L.
Li
,
G. L.
Richmong
,
J. S.
Francisco
, and
X. C.
Zeng
,
J. Am. Chem. Soc.
139
,
17168
17174
(
2017
).
7.
M. T. C.
Martins-Costa
,
J. M.
Anglada
,
J. S.
Francisco
, and
M. F.
Ruiz-Lopez
,
J. Am. Chem. Soc.
140
,
12341
12344
(
2018
).
8.
T. E.
Dermota
,
D. P.
Hydutsky
,
N. J.
Biamco
, and
A. W.
Castleman
,
J. Phys. Chem. A
109
,
8254
8258
(
2005
).
9.
F.
Dong
,
S.
Heinbuch
,
J. J.
Rocca
, and
E. R.
Bernstein
,
J. Chem. Phys.
125
,
154317
(
2006
).
10.
J. A.
Kroll
,
B. N.
Frandsen
,
H. G.
Kjaergaard
, and
V.
Vaida
,
J. Phys. Chem. A
122
(
18
),
4465
4469
(
2018
).
11.
J. M.
Anglada
,
M. T.
Martins-Costa
,
J. S.
Francisco
, and
M. F.
Ruiz-López
,
Phys. Chem. Chem. Phys.
21
,
9779
(
2019
).
12.
B.
Wang
and
H.
Hou
,
Chem. Phys. Lett.
410
,
235
(
2005
).
13.
C. L.
Ramussen
,
P.
Glarborg
, and
P.
Marshall
,
Proc. Combust. Inst.
31
,
339
(
2007
).
14.
M.
Wierzejewska
and
A.
Olbert-Majkut
,
J. Phys. Chem. A
111
,
2790
2796
(
2007
).
15.
M. Y.
Ballester
and
A. J. C.
Varandas
,
Chem. Phys. Lett.
433
,
279
(
2007
).
16.
M. Y.
Ballester
and
A. J. C.
Varandas
,
Phys. Chem. Chem. Phys.
7
(
11
),
2305
2317
(
2005
).
17.
B.
Napolion
and
J. D.
Watts
,
Chem. Phys. Lett.
421
,
562
565
(
2006
).
18.
J.-X.
Qi
,
W.-Q.
Deng
,
K.-L.
Han
, and
G. Z.
He
,
J. Chem. Soc., Faraday Trans.
93
,
25
28
(
1997
).
19.
R. C.
Fortenberry
,
J. S.
Francisco
, and
T. J.
Lee
,
J. Phys. Chem. A
121
(
42
),
8108
8114
(
2017
).
20.
S. E.
Wheeler
and
H. F.
Schaefer
 III
,
J. Phys. Chem. A
113
(
24
),
6779
6788
(
2009
).
21.
M. C.
McCarthy
,
V.
Lattanzi
,
O.
Martinez
, Jr.
,
J.
Gauss
, and
S.
Thorwirth
,
J. Phys. Chem. Lett.
4
(
23
),
4074
4079
(
2013
).
22.
E.
Isoniemi
,
L.
Khriachtchev
,
J.
Lundell
, and
M.
Rasanen
,
Phys. Chem. Chem. Phys.
4
(
9
),
1549
1554
(
2002
).
23.
T.
Trabelsi
,
S. B.
Yaghlane
,
M. M.
Al Mogren
,
J. S.
Francisco
, and
M.
Hochlaf
,
J. Chem. Phys.
145
,
084307
(
2016
).
24.
T.
Trabelsi
,
M.
Kumar
, and
J. S.
Francisco
,
J. Am. Chem. Soc.
139
(
43
),
15446
15449
(
2017
).
25.
P. J.
Knowles
and
H.-J.
Werner
,
Chem. Phys. Lett.
115
,
259
(
1985
).
26.
H.-J.
Werner
and
P. J.
Knowles
,
J. Chem. Phys.
82
,
5053
(
1985
).
27.
H.-J.
Werner
and
P. J.
Knowles
,
J. Chem. Phys.
89
,
5803
(
1988
).
28.
P. J.
Knowles
and
H.-J.
Werner
,
Chem. Phys. Lett.
145
,
514
(
1988
).
29.
P. G.
Szalay
and
R. J.
Bartlett
,
Chem. Phys. Lett.
214
,
481
(
1993
).
30.
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
90
,
1007
(
1989
).
31.
D. E.
Woon
and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
98
,
1358
(
1993
).
32.
K.
Suma
,
Y.
Sumiyoshi
, and
Y.
Endo
,
Science
308
(
5730
),
1885
1886
(
2005
).
33.
A.
Mansergas
,
J. M.
Anglada
,
S.
Olivella
,
M. F.
Ruiz-López
, and
M.
Martins-Costa
,
Phys. Chem. Chem. Phys.
9
(
44
),
5865
5873
(
2007
).
34.
L. P.
Viegas
,
D.
Carolina
, and
A. J.
Varandas
,
Chem. Phys. Lett.
620
,
61
66
(
2015
).
35.
S. D.
Le Picard
,
M.
Tizniti
,
A.
Canosa
,
I. R.
Sims
, and
I. W.
Smith
,
Science
328
(
5983
),
1258
1262
(
2010
).
36.
J. M.
Anglada
,
S.
Olivella
, and
A.
Solé
,
J. Chem. Theory Comput.
6
(
9
),
2743
2750
(
2010
).
37.
A. J. C.
Varandas
,
Phys. Chem. Chem. Phys.
13
(
34
),
15619
15623
(
2011
).
38.
M. H.
Palmer
,
D. A.
Shaw
, and
M. F.
Guest
,
Mol. Phys.
103
(
6-8
),
1183
1200
(
2005
).
39.
S.
Saito
,
J. Chem. Phys.
53
(
6
),
2544
2545
(
1970
).

Supplementary Material

You do not currently have access to this content.