The seam of conical intersection of two electronic states is said to be curved when the span of the basis vectors describing the branching plane varies along the seam. In this work degenerate perturbation theory is used to determine an approximately diabatic Hamiltonian that can reliably reproduce the potential-energy surfaces in the vicinity of a point of conical intersection. This Hamiltonian provides a rigorous description of seam curvature, and a means for obtaining the full -dimensional seam of conical intersection connected to a point of conical intersection.
REFERENCES
1.
G. J.
Atchity
, S. S.
Xantheas
, and K.
Ruedenberg
, J. Chem. Phys.
95
, 1862
(1991
).2.
R.
Englman
, The Jahn-Teller Effect in Molecules and Crystals
(Wiley-Interscience
, New York, 1972
).3.
D. R.
Yarkony
, J. Chem. Phys.
112
, 2111
(2000
).4.
D. R.
Yarkony
, J. Phys. Chem. A
101
, 4263
(1997
).5.
M. J.
Paterson
, M. J.
Bearpark
, M. A.
Robb
, and L.
Blancafort
, J. Chem. Phys.
121
, 11562
(2004
).6.
I.
Shavitt
, in Modern Theoretical Chemistry
, edited by H. F.
Schaefer
(Plenum
, New York, 1976
), Vol. 3
, p. 189
.7.
8.
R. A.
Young
, Jr. and D. R.
Yarkony
, J. Chem. Phys.
123
, 085315
(2005
).9.
C. A.
Mead
, J. Chem. Phys.
78
, 807
(1983
).10.
H.
Lischka
, M.
Dallos
, P.
Szalay
, D. R.
Yarkony
, and R.
Shepard
, J. Chem. Phys.
120
, 7322
(2004
).11.
M. R.
Hoffman
, D. J.
Fox
, J. F.
Gaw
, Y.
Osamura
, Y.
Yamaguchi
, R. S.
Grev
, G.
Fitzgerald
, H. F.
Schaefer
, P. J.
Knowles
, and N. C.
Handy
, J. Chem. Phys.
80
, 2660
(1984
).12.
B. H.
Lengsfield
and D. R.
Yarkony
, J. Chem. Phys.
84
, 348
(1986
);13.
S.
Han
and D. R.
Yarkony
, in Conical Intersections
, edited by G. A.
Worth
and S.
Althorpe
(CCP6
, London, 2004
).14.
C. A.
Mead
and D. G.
Truhlar
, J. Chem. Phys.
77
, 6090
(1982
).15.
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
, p. 1
.16.
H.
Lischka
, R.
Shepard
, I.
Shavitt
et al., COLUMBUS, an ab initio electronic structure program (Argonne National Laboratory, Argonne, IL, 2004
).17.
D. R.
Yarkony
, J. Chem. Phys.
114
, 2601
(2001
).© 2005 American Institute of Physics.
2005
American Institute of Physics
You do not currently have access to this content.
