On the ultraviolet photofragmentation of CH3Xe

作者：Alekseyev Aleksey B^*; Liebermann Heinz Peter; Buenker Robert J

来源：Journal of Chemical Physics, 2009, 130(2): 024309.

DOI：10.1063/1.3055909

• bond angles
• bond lengths
• configuration interactions
• excited states
• Franck-Condon factors
• ground states
• molecule-photon collisions
• organic compounds
• photodissociation
• positive ions
• potential energy surfaces
• spin-orbit interactions
• transition moments

The multireference spin-orbit configuration interaction method is employed to calculate potential energy surfaces for the ground and low-lying excited states of the CH3Xe 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 CH3Xe is well bound (D-e=1.78 eV) and dissociates to the CH3 (X (1)A(1)(')) Xe(S-1) limit. In contrast, all lowest excited states of CH3Xe are repulsive in the Franck-Condon region and converge to the strongly spin-split CH3(X (2)A(')) Xe (P-2(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 CH3Xe is dominated by the parallel (3)Q(0)( )(A(1))<- X (1)A(1) transition, which leads to the CH3 Xe (P-2(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 CH3Xe 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 CH3I systems.

• 出版日期2009-1-14