On the ultraviolet photofragmentation of CH3Xe+.
The multireference spin-orbit configuration interaction method is employed to calculate potential energy surfaces for the ground and low-lying excited states of the CH(3)Xe(+) cation as functions of the Xe-C bond length and the Xe-C-H angle. It is shown that the X (1)A(1) ground state of CH(3)Xe(+) is well bound (D(e)=1.78 eV) and dissociates to the CH(3)(+)(X (1)A(1)(')) + Xe((1)S) limit. In contrast, all lowest excited states of CH(3)Xe(+) are repulsive in the Franck-Condon region and converge to the strongly spin-split CH(3)(X (2)A(")) + Xe(+)((2)P(3/2,1/2)) asymptotes. Transition dipole moments for the low-lying valence states are computed at the X (1)A(1) equilibrium geometry. It is shown that the first absorption continuum (A band) of CH(3)Xe(+) is dominated by the parallel (3)Q(0(+))(A(1)) <-- X (1)A(1) transition, which leads to the CH(3) + Xe(+)((2)P(3/2)) dissociation products. The perpendicular transitions to the (1)Q(E), (3)Q(1)(E), and (3)A(1)(E) states are found to be significantly weaker. The CH(3)Xe(+) photodissociation process in its A band is analyzed on the basis of the computed data and compared with the photodissociation of the isovalent RgH(+) (Rg = Ar,Kr,Xe), HI, and CH(3)I systems.
Alekseyev
Aleksey B
AB
Fachbereich C, Theoretische Chemie, Bergische Universität Wuppertal, Gausstr. 20, D-42097 Wuppertal, Germany. alexeev@uni-wuppertal.de
Liebermann
Heinz-Peter
HP
Buenker
Robert J
RJ