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Journal Article

Spin-Orbit Coupling and the Intersection of Potential Energy Surfaces in Polyatomic Molecules

A. J. Stone
Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences
Vol. 351, No. 1664 (Oct. 8, 1976), pp. 141-150
Published by: Royal Society
Stable URL: http://www.jstor.org/stable/79314
Page Count: 10
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Spin-Orbit Coupling and the Intersection of Potential Energy Surfaces in Polyatomic Molecules
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Abstract

Longuet-Higgins' theorem, which shows that the existence of intersections between potential energy surfaces may be deduced from the behaviour of the wavefunction at points remote from the intersection, is generalized to cover cases where the Hamiltonian is complex. It is concluded that an intersection due to symmetry in one region of nuclear configuration space may imply that the same surfaces intersect over a region of higher dimension and lower symmetry where their wavefunctions belong to the same symmetry species. It is shown that this behaviour occurs in d1 octahedral complexes in the presence of spin-orbit coupling.

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