Hyperspherical nuclear motion of H3 + and D3 + in the electronic triplet state, a 3Sigmau +.
The potential energy surface of H(3) (+) in the lowest electronic triplet state, a (3)Sigma(u) (+), shows three equivalent minima at linear nuclear configurations. The vibrational levels of H(3) (+) and D(3) (+) on this surface can therefore be described as superimposed linear molecule states. Owing to such a superposition, each vibrational state characterized by quantum numbers of an isolated linear molecule obtains a one- and a two-dimensional component. The energy splittings between the two components have now been rationalized within a hyperspherical picture. It is shown that nuclear motion along the hyperangle phi mainly accounts for the splittings and provides upper bounds. This hyperspherical motion can be considered an extension of the antisymmetric stretching motion of the individual linear molecule.
Ferreira
Tiago Mendes
TM
Departamento de Química, Universidade de Coimbra, 3004-535 Coimbra, Portugal.
Alijah
Alexander
A
Varandas
António J C
AJ