A global reaction route map is generated for Au5 by the anharmonic downward distortion following method in which 5 minima and 14 transition states (TSs) are located. Through vibrational analyses in the 3N − 7 (N = 5) dimensional space orthogonal to the intrinsic reaction coordinate (IRC), along all the IRCs, four IRCs are found to have valley-ridge transition (VRT) points on the way where a potential curvature changes its sign from positive to negative in a direction orthogonal to the IRC. The detailed mechanisms of bifurcations related to the VRTs are discussed by surveying a landscape of the global reaction route map, and the connectivity of VRT points and minima is clarified. Branching of the products through bifurcations is confirmed by ab initio molecular dynamics simulations starting from the TSs. A new feature of the reaction pathways, unification, is found and discussed.

1.
K.
Fukui
,
J. Phys. Chem.
74
,
4161
(
1970
).
2.
K.
Ohno
and
S.
Maeda
,
Chem. Phys. Lett.
384
,
277
(
2004
).
3.
S.
Maeda
and
K.
Ohno
,
J. Phys. Chem. A
109
,
5742
(
2005
).
4.
K.
Ohno
and
S.
Maeda
,
J. Phys. Chem. A
110
,
8933
(
2006
).
5.
S.
Maeda
,
K.
Ohno
, and
K.
Morokuma
,
Phys. Chem. Chem. Phys.
15
,
3683
(
2013
).
6.
S.
Maeda
,
T.
Taketsugu
,
K.
Morokuma
, and
K.
Ohno
,
Bull. Chem. Soc. Jpn.
87
,
1315
(
2014
).
7.
S.
Maeda
and
K.
Morokuma
,
J. Chem. Theory Comput.
7
,
2335
(
2011
).
8.
S.
Maeda
,
T.
Taketsugu
, and
K.
Morokuma
,
J. Comput. Chem.
35
,
166
(
2014
).
9.
P.
Valtazanos
and
K.
Ruedenberg
,
Theor. Chim. Acta
69
,
281
(
1986
).
10.
J.
Baker
and
P. M. W.
Gill
,
J. Comput. Chem.
9
,
465
(
1988
).
11.
P.
Valtazanos
,
S. T.
Elbert
,
S.
Xantheas
, and
K.
Ruedenberg
,
Theor. Chim. Acta
78
,
287
(
1991
).
12.
T.
Taketsugu
,
N.
Tajima
, and
K.
Hirao
,
J. Chem. Phys.
105
,
1933
(
1996
).
13.
T.
Yanai
,
T.
Taketsugu
, and
K.
Hirao
,
J. Chem. Phys.
107
,
1137
(
1997
).
14.
T.
Taketsugu
,
T.
Yanai
,
K.
Hirao
, and
M. S.
Gordon
,
J. Mol. Struct.: THEOCHEM
451
,
163
(
1998
).
15.
S.
Maeda
,
Y.
Harabuchi
,
Y.
Ono
,
T.
Taketsugu
, and
K.
Morokuma
,
Int. J. Quantum Chem.
115
,
258
(
2015
).
16.
Y.
Harabuchi
,
A.
Nakayama
, and
T.
Taketsugu
,
Comput. Theor. Chem.
1000
,
70
(
2012
).
17.
H.
Metiu
,
J.
Ross
,
R.
Silbey
, and
T. F.
George
,
J. Chem. Phys.
61
,
3200
(
1974
).
18.
A.
Tachibana
,
I.
Okazaki
,
M.
Koizumi
,
K.
Hori
, and
T.
Yamabe
,
J. Am. Chem. Soc.
107
,
1190
(
1985
).
19.
M. V.
Basilevsky
,
Theor. Chim. Acta
72
,
63
(
1987
).
21.
J. M.
Bofill
and
W.
Quapp
,
J. Math. Chem.
51
,
1099
(
2013
).
22.
W.
Quapp
,
Theor. Chim. Acta
75
,
447
(
1989
).
23.
T.
Taketsugu
and
T.
Hirano
,
J. Chem. Phys.
99
,
9806
(
1993
).
24.
T.
Taketsugu
and
T.
Hirano
,
J. Mol. Struct.: THEOCHEM
116
,
169
(
1994
).
25.
H. B.
Schlegel
,
J. Chem. Soc., Faraday Trans.
90
,
1569
(
1994
).
26.
G. N.
Sastry
and
S.
Shaik
,
J. Phys. Chem.
100
,
12241
(
1996
).
27.
S.
Shaik
,
D.
Danovich
,
G. N.
Sastry
,
P. Y.
Ayala
, and
H. B.
Schlegel
,
J. Am. Chem. Soc.
119
,
9237
(
1997
).
28.
H.
Yamataka
,
M.
Aida
, and
M.
Dupuis
,
Chem. Phys. Lett.
300
,
583
(
1999
).
29.
Y.
Kumeda
and
T.
Taketsugu
,
J. Chem. Phys.
113
,
477
(
2000
).
30.
T.
Taketsugu
and
Y.
Kumeda
,
J. Chem. Phys.
114
,
6973
(
2001
).
31.
J.
Li
,
X. S.
Li
,
S.
Shaik
, and
H. B.
Schlegel
,
J. Phys. Chem. A
108
,
8526
(
2004
).
32.
J.
Li
,
S.
Shaik
, and
H. B.
Schlegel
,
J. Phys. Chem. A
110
,
2801
(
2006
).
33.
J. M.
Ramirez-Anguita
,
R.
Gelabert
,
A.
Gonzalez-Lafont
,
M.
Moreno
, and
J. M.
Lluch
,
Theor. Chem. Acc.
128
,
569
(
2011
).
34.
Y.
Harabuchi
and
T.
Taketsugu
,
Theor. Chem. Acc.
130
,
305
(
2011
).
35.
M.
Haruta
,
T.
Kobayashi
,
H.
Sano
, and
N.
Yamada
,
Chem. Lett.
16
,
405
(
1987
).
36.
M.
Gao
,
A.
Lyalin
, and
T.
Taketsugu
,
Int. J. Quantum Chem.
113
,
443
(
2013
).
37.
M.
Gao
,
A.
Lyalin
, and
T.
Taketsugu
,
J. Chem. Phys.
138
,
034701
(
2013
).
38.
M.
Gao
,
A.
Lyalin
,
S.
Maeda
, and
T.
Taketsugu
,
J. Chem. Theory Comput.
10
,
1623
(
2014
).
39.
W. H.
Miller
,
N. C.
Handy
, and
J. E.
Adams
,
J. Chem. Phys.
72
,
99
(
1980
).
40.
S.
Kato
and
K.
Morokuma
,
J. Chem. Phys.
73
,
3900
(
1980
).
41.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
,
G. E.
Scuseria
,
M. A.
Robb
 et al, gaussian 09, Revision D.01,
Gaussian, Inc.
,
Wallingford, CT
,
2009
.
42.
S.
Maeda
,
Y.
Osada
,
K.
Morokuma
, and
K.
Ohno
, GRRM11, version 11.01, 2011.
43.
S.
Maeda
,
Y.
Osada
,
Y.
Harabuchi
,
T.
Taketsugu
,
K.
Morokuma
 et al, GRRM, a developmental version at Hokkaido University, Sapporo, Japan, 2015.
44.
Y.
Harabuchi
,
M.
Okai
,
R.
Yamamoto
,
Y.
Ono
, and
T.
Taketsugu
, SPPR, a developmental version at Hokkaido University, Sapporo, Japan, 2015.
45.
P.
Pyykkö
,
Angew. Chem., Int. Ed.
43
,
4412
(
2004
).
You do not currently have access to this content.