Three-dimensional analytical infinite order sudden quantum theory for triatomic indirect photodissociation processes

• Autores: Grinberg, H.; Freed, K.F.; Williams, C.J.
• Año de publicación: 1997
• Idioma: inglés
• Tipo de recurso: artículo
• Fuente: J Chem Phys 1997;107(6):1835-1848
• Materia: Approximation theory; Calculations; Dissociation; Electron energy levels; Perturbation techniques; Photochemical reactions; Three dimensional; Indirect photodissociation processes; Three dimensional infinite order sudden quantum theory; Triatomic photodissociation; Quantum theory
• Institución: Universidad Nacional de Buenos Aires. Facultad de Ciencias Exactas y Naturales

Our previously developed analytical infinite order sudden (IOS) quantum theory of triatomic photodissociation is extended to describe indirect photodissociation processes through a real or virtual intermediate state. The theory uses the IOS approximation for the dynamics in the final dissociative channels and an Airy function approximation for the continuum states. These approximations enable us to evaluate the multi-dimensional non-separable transition amplitudes analytically (as one-dimensional quadratures), despite the different natural coordinates for the initial bound, the intermediate resonant, and the final dissociative states. The fragment internal energy distributions are described as a function of the initial and final quantum states and the photon excitation energy. The theory readily permits the evaluation of rotational distributions for high values of the total angular momentum J in the initial bound molecular state, a feature that would be very difficult with close-coupled methods. In paper II we apply the theory to describe the photofragment yield spectrum of NOCl in the region of the T1(13A″)→S0(11A′) transition. © 1997 American Institute of Physics.
Fil:Grinberg, H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina.