The E1 electronic state of cyclic N3+ arising from the singly excited electron configuration e3e is studied using multireference configuration interaction wave functions and a quadratic Jahn-Teller Hamiltonian determined from those calculations. It is shown that these two states have both a symmetry-required seam of conical intersections at D3h geometries and three proximal symmetry equivalent C2v seams, located on a circle with radius ρ0 from the D3h intersection. ρ0, a function of Qs, the breathing mode, is quite small but only attains a value of zero at Qscrit=1.252Å, resulting in a confluence or intersection node of the three C2v seams with the D3h seam. At this point only, g=g(Qs), the norm of half the energy difference gradient, the linear Jahn-Teller term, vanishes and the intersection is of the Renner-Teller type. The close proximity of the previously unreported C2v seams to the D3h seam over the range of Qs considered is a consequence of the small values of g, compared to the quadratic Jahn-Teller term. The present analysis has important implications in the study of Jahn-Teller effects in ring systems and provides insight into a recent report that characterized this D3h seam as a Renner-Teller or glancing intersection.

1.
M. T.
Nguyen
,
Coord. Chem. Rev.
244
,
93
(
2003
).
2.
T. W.
Archibald
and
J. R.
Sabin
,
J. Phys. Chem.
55
,
1821
(
1971
);
C.
Petrongolo
,
J. Mol. Struct.
175
,
215
(
1988
);
J. M. L.
Martin
,
J. P.
Francois
, and
R.
Gijbels
,
J. Chem. Phys.
90
,
6049
(
1989
);
F.
Tarantelli
,
L. S.
Cederbaum
, and
P.
Campos
,
J. Chem. Phys.
91
,
7039
(
1989
);
J. M. L.
Martin
,
J. P.
Francois
, and
R.
Gijbels
,
Chem. Phys. Lett.
166
,
295
(
1990
);
J. M. L.
Martin
,
J. P.
Francois
, and
R.
Gijbels
,
J. Chem. Phys.
93
,
4485
(
1990
);
G.
Chambaud
and
P.
Rosmus
,
J. Chem. Phys.
96
,
77
(
1992
).
3.
B. A.
Thrush
,
Proc. R. Soc. London, Ser. A
235
,
143
(
1956
);
C. R.
Braizer
,
P. F.
Bernath
,
J. B.
Burkholder
, and
C. J.
Howard
,
J. Chem. Phys.
89
,
1762
(
1988
);
R. E.
Continetti
,
D. R.
Cyr
,
R. B.
Metz
, and
D. M.
Neumark
,
Chem. Phys. Lett.
182
,
406
(
1991
);
R. E.
Continetti
,
D. R.
Cyr
,
D. L.
Osborn
,
D. J.
Leahy
, and
D. M.
Neumark
,
J. Chem. Phys.
99
,
2616
(
1993
);
M. J.
Pellerite
,
R. L.
Jackson
, and
J. I.
Brauman
,
J. Phys. Chem.
85
,
1624
(
1981
).
4.
J.
Wasilewski
,
J. Chem. Phys.
105
,
10969
(
1996
);
Y.
Byun
,
S.
Saebo
, and
C.
Pittman
, Jr.
,
J. Am. Chem. Soc.
113
,
3689
(
1991
).
5.
M.
Bittererova
,
H.
Ostmark
, and
T.
Brinck
,
J. Chem. Phys.
116
,
9740
(
2002
).
6.
P.
Zhang
,
K.
Morokuma
, and
A. M.
Wodtke
,
J. Chem. Phys.
122
,
014106
(
2005
).
7.
N.
Hansen
and
A. M.
Wodtke
,
J. Phys. Chem. A
107
,
10608
(
2003
);
N.
Hansen
,
A. M.
Wodtke
,
S. J.
Goncher
,
J. C.
Robinson
,
N. E.
Sveum
, and
D. M.
Neumark
,
J. Chem. Phys.
123
,
104305
(
2005
);
[PubMed]
P. C.
Samartzis
,
J. J. M.
Lin
,
T. T.
Ching
,
C.
Chaudhuri
,
Y. T.
Lee
,
S. H.
Lee
, and
A. M.
Wodtke
,
J. Chem. Phys.
123
,
051101
(
2005
).
[PubMed]
8.
D.
Babikov
,
P.
Zhang
, and
K.
Morokuma
,
J. Chem. Phys.
121
,
6743
(
2004
);
[PubMed]
D.
Babikov
,
B.
Kendrick
,
P.
Zhang
, and
K.
Morokuma
,
J. Chem. Phys.
122
,
044315
(
2005
).
9.
R.
Tarroni
and
P.
Tosi
,
Chem. Phys. Lett.
389
,
274
(
2004
).
10.
V. A.
Mozhayskiy
,
D.
Babikov
, and
A. I.
Krylov
,
J. Chem. Phys.
124
,
224309
(
2006
).
11.
P. J.
Kuntz
and
W. N.
Whitton
,
J. Chem. Phys.
95
,
5149
(
1991
);
P. J.
Kuntz
,
W. N.
Whitton
,
I.
Paidarova
, and
R.
Polak
,
Can. J. Chem.
72
,
939
(
1994
);
M. J.
Paterson
,
M. J.
Bearpark
,
M. A.
Robb
,
L.
Blancafort
, and
G. A.
Worth
,
Phys. Chem. Chem. Phys.
7
,
2100
(
2005
).
[PubMed]
12.
G. J.
Atchity
,
K.
Ruedenberg
, and
A.
Nanayakkara
,
Theor. Chem. Acc.
96
,
195
(
1997
).
13.
D. R.
Yarkony
,
J. Chem. Phys.
123
,
204101
(
2005
).
14.
J. W.
Zwanziger
and
E. R.
Grant
,
J. Chem. Phys.
87
,
2954
(
1987
).
15.
H.
Köppel
and
R.
Meiswinkel
,
Z. Phys. D: At., Mol. Clusters
32
,
153
(
1994
).
16.
R.
Englman
,
The Jahn-Teller Effect in Molecules and Crystals
(
Wiley-Interscience
,
New York
,
1972
).
17.
E. R.
Bernstein
and
J. D.
Webb
,
Mol. Phys.
35
,
1585
(
1978
);
G. R.
Meredith
,
J. D.
Webb
, and
E. R.
Bernstein
,
Mol. Phys.
34
,
955
(
1978
);
J. D.
Webb
,
K. M.
Swift
, and
E. R.
Bernstein
,
J. Chem. Phys.
73
,
4891
(
1980
).
18.
G. J.
Atchity
and
K.
Ruedenberg
,
Theor. Chem. Acc.
97
,
176
(
1997
).
19.
D. R.
Yarkony
,
Theor. Chem. Acc.
98
,
197
(
1997
).
20.
D. R.
Yarkony
,
J. Chem. Phys.
111
,
4906
(
1999
).
21.
R. G.
Sadygov
and
D. R.
Yarkony
,
J. Chem. Phys.
110
,
3639
(
1999
).
22.
H.
Lischka
,
M.
Dallos
,
P.
Szalay
,
D. R.
Yarkony
, and
R.
Shepard
,
J. Chem. Phys.
120
,
7322
(
2004
).
23.
M.
Dallos
,
H.
Lischka
,
P.
Szalay
,
R.
Shepard
, and
D. R.
Yarkony
,
J. Chem. Phys.
120
,
7330
(
2004
).
24.
T. C.
Thompson
,
G.
Izmirlian
,
S. J.
Lemon
,
D. G.
Truhlar
, and
C. A.
Mead
,
J. Chem. Phys.
82
,
5597
(
1985
).
25.
G. J.
Atchity
,
S. S.
Xantheas
, and
K.
Ruedenberg
,
J. Chem. Phys.
95
,
1862
(
1991
).
26.
D. R.
Yarkony
,
Acc. Chem. Res.
31
,
511
(
1998
).
27.
C. A.
Mead
,
J. Chem. Phys.
78
,
807
(
1983
);
I.
Bersuker
,
The Jahn-Teller effect
(
Cambridge University Press
,
Cambridge
,
2006
).
28.
B. H.
Lengsfield
and
D. R.
Yarkony
, in
State-Selected and State to State Ion-Molecule Reaction Dynamics, Part 2: Theory
, edited by
M.
Baer
and
C.-Y.
Ng
(
Wiley
,
New York
,
1992
), Vol.
82
, pp.
1
.
29.
A.
Ceulemans
,
Chem. Phys.
66
,
169
(
1982
).
30.
P.
Garcia-Fernandez
,
I. B.
Bersuker
, and
J. E.
Boggs
,
J. Chem. Phys.
125
,
104102
(
2006
).
31.
H.
Lischka
,
R.
Shepard
,
I.
Shavitt
 et al, COLUMBUS, an ab initio electronic structure program,
2003
.
32.
H.
Köppel
,
W.
Domcke
, and
L. S.
Cederbaum
,
Adv. Chem. Phys.
57
,
59
(
1984
).
33.
F.
Cocchini
,
T. H.
Upton
, and
W.
Andreoni
,
J. Chem. Phys.
88
,
6068
(
1988
).
34.
A.
Ceulemans
,
L. F.
CHibotaru
,
P. W.
Fowler
, and
M.
Szopa
,
J. Chem. Phys.
110
,
6916
(
1999
).
35.
M.
Schuurman
and
D. R.
Yarkony
,
J. Chem. Phys.
126
,
044104
(
2007
).
You do not currently have access to this content.