The effects of nonadiabatic interactions attributable to a seam of conical intersections on the electronic structure of the 1,22A states of hydroxymethoxy (HO)CH2O is explored. Illuminating comparisons are made between hydroxymethoxy and ethoxy and isopropoxy, all of which can be thought of as substitutional isomers of the methoxy radical. Surprisingly, the potential energy surfaces and conical topographies for hydroxymethoxy are shown to be dramatically different from those evidenced in ethoxy or isopropoxy radicals, dissimilarities traced to the hydroxyl group. Also considered in this study was the feasibility of representing the coupled 1,22A adiabatic electronic states of hydroxymethoxy within the vibronic coupling approximation using a quasi-diabatic Hamiltonian and subsequently using that representation to simulate the photoelectron spectrum of the hydroxymethoxide anion. Complications attributable to the torsional motion of the hydroxyl hydrogen are analyzed.

1.
F.
Bernardi
,
M.
Olivucci
, and
M. A.
Robb
,
Chem. Soc. Rev.
25
,
321
(
1996
).
2.
F.
Bernardi
,
M.
Olivucci
, and
M. A.
Robb
,
J. Photochem. Photobiol. A
105
,
365
(
1997
).
3.
D. R.
Yarkony
,
Rev. Mod. Phys.
68
,
985
(
1996
).
4.
M.
Klessinger
and
J.
Michl
,
Excited States and the Photochemistry of Organic Molecules
(
VCH
,
New York
,
1995
).
5.
I.
Baldea
,
J.
Franz
, and
H.
Köppel
,
Chem. Phys.
329
,
65
75
(
2006
).
6.
T.
Ichino
,
A. J.
Gianola
,
W. C.
Lineberger
, and
J. F.
Stanton
,
J. Chem. Phys.
125
,
084312
(
2006
).
7.
M. S.
Schuurman
and
D. R.
Yarkony
,
J. Chem. Phys.
129
,
064304
(
2008
).
8.
J.
Dillon
,
D. R.
Yarkony
, and
M. S.
Schuurman
,
J. Chem. Phys.
134
,
184314
(
2011
).
9.
T. M.
Ramond
,
G. E.
Davico
,
R. L.
Schwartz
, and
W. C.
Lineberger
,
J. Chem. Phys.
112
,
1158
(
2000
).
10.
C. C.
Carter
,
J. R.
Atwell
,
S.
Gopalakrishnan
, and
T. A.
Miller
,
J. Phys. Chem. A
104
(
40
),
9165
(
2000
).
11.
J.
Jin
,
I.
Sioutis
,
G.
Tarczay
,
S.
Gopalakrishnan
,
A.
Bezanat
, and
T. A.
Miller
,
J. Chem. Phys.
121
,
11780
(
2004
).
12.
S.
Gopalakrishnan
,
L.
Zu
, and
T. A.
Miller
,
Chem. Phys. Lett.
380
,
749
(
2003
).
13.
G.
Tarczay
,
S.
Gopalakrishnan
, and
T. A.
Miller
,
J. Mol. Spec.
220
,
276
(
2003
).
14.
H.
Choi
,
R. T.
Bise
, and
D. M.
Neumark
,
J. Phys. Chem. A
104
(
45
),
10112
(
2000
).
15.
J. J.
Dillon
and
D. R.
Yarkony
,
J. Chem. Phys.
131
,
134303
(
2009
).
16.
D. M.
Neumark
,
J. Phys. Chem. A
112
,
13287
(
2008
).
17.
J. J.
Dillon
and
D. R.
Yarkony
,
J. Chem. Phys.
130
,
154312
(
2009
).
18.
I.
Bersuker
,
The Jahn-Teller Effect
(
Cambridge University Press
,
Cambridge
,
2006
).
19.
G. J.
Atchity
,
S. S.
Xantheas
, and
K.
Ruedenberg
,
J. Chem. Phys.
95
,
1862
(
1991
).
20.
D. R.
Yarkony
,
Acc. Chem. Res.
31
,
511
(
1998
).
21.
E.
Henon
,
F.
Bohr
,
N.
Sokolowski-Gomez
, and
F.
Caralp
,
Phys. Chem. Chem. Phys.
5
,
5431
(
2003
).
22.
W.
Eisfeld
and
J.
Francisco
,
J. Chem. Phys.
131
,
134313
(
2009
).
23.
X.
Zhu
and
D. R.
Yarkony
,
J. Chem. Phys.
132
,
104101
(
2010
).
24.
J. J.
Dillon
,
D. R.
Yarkony
, and
M. S.
Schuurman
,
J. Chem. Phys.
134
,
044101
(
2011
).
25.
M.
Dallos
,
H.
Lischka
,
P.
Szalay
,
R.
Shepard
, and
D. R.
Yarkony
,
J. Chem. Phys.
120
,
7330
(
2004
).
26.
H.
Lischka
,
M.
Dallos
,
P.
Szalay
,
D. R.
Yarkony
, and
R.
Shepard
,
J. Chem. Phys.
120
,
7322
(
2004
).
27.
See supplementary material at http://dx.doi.org/10.1063/1.4757727 for supplementary tables and figures.
28.
D. R.
Yarkony
,
J. Phys. Chem. A
101
,
4263
(
1997
).
29.
D. R.
Yarkony
,
J. Chem. Phys.
112
,
2111
(
2000
).
30.
H.
Köppel
,
W.
Domcke
, and
L. S.
Cederbaum
, in
Conical Intersections
, edited by
W.
Domcke
,
D. R.
Yarkony
, and
H.
Köppel
(
World Scientific
,
New Jersey
,
2004
), Vol. 15, p.
323
.
31.
X.
Zhu
and
D. R.
Yarkony
,
J. Chem. Phys.
137
,
22A511
(
2012
).
32.
X.
Zhu
and
D. R.
Yarkony
,
J. Chem. Phys.
136
,
174110
(
2012
).
33.
C. A.
Mead
and
D. G.
Truhlar
,
J. Chem. Phys.
77
,
6090
(
1982
).
34.
T. I.
Yacovitch
,
J. B.
Kim
,
E.
Garand
,
D. G.
van der Poll
, and
D. M.
Neumark
,
J. Chem. Phys.
134
,
134307
(
2011
).
35.
G.
Fogarasi
,
X.
Zhou
,
P. W.
Taylor
, and
P.
Pulay
,
J. Am. Chem. Soc.
114
,
8191
(
1992
).

Supplementary Material

You do not currently have access to this content.