Electronic and vibrational predissociation in ArI[sub 2] photodissociation dynamics

Lepetit, Bruno; Roncero, Octavio; Buchachenko, Alexei A.; Halberstadt, Nadine
May 2002
Journal of Chemical Physics;5/15/2002, Vol. 116 Issue 19, p8367
Academic Journal
Quantum dynamical calculations on the photodissociation process: ArI[sub 2](X) + h v→Ar+ I[sub 2](B) or Ar+ I+I have been performed using diatomics-in-molecule semiempirical potential energy surfaces in the spectral region of the I[sub 2](B,v = 15-25)←I[sub 2](X,v = 0) transition. The B state responsible for vibrational predissociation producing Ar+I[sub 2](B) is coupled to four dissociative states inducing electronic predissociation to Ar+I(²P[sub 3/2])+I(²P[sub 3/2]). These dissociative states correlate to the a(lg), a′(0g[sup +]), B″(1u), l(2g) electronic states of I[sub 2]. Both linear and perpendicular initial ArI[sub 2](X) isomers are considered. For the linear isomer, only the a′ state has non-negligible effect on photodissociation dynamics, although total photon absorption cross sections are not significantly modified when coupling to a′ is taken into account, partial cross sections corresponding to vibrational predissociation are smaller. For the perpendicular isomer, resonance decay rates are increased, mainly by the coupling to a′ (0g[sup +]), 1 (2g), and a(1g) states. Decay rates oscillate as a function of the vibrational excitation of I[sub 2] (B) but the main source of oscillation is the intramolecular vibrational energy redistribution which occurs in vibrational predissociation, rather than Franck-Condon oscillations in electronic predissociation.


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