Theoretical investigation of the photodissociation dynamics by the decay of a non-dissociative excited state: application to core-excited N2

A theoretical model for the description of the vibrationally resolved photodissociation of diatomic molecules through the decay of bonding core-excited states is proposed and applied to the photodissociation induced by the highly resolved resonant N1s → 1 πg core excitation of an isolated N2 followed by spectator Auger decay to an excited state of N2+ which may dissociate. The photodissociation and absorption spectra are distinctly different. The absorption spectrum extracted from the model agrees with experimental data. The kinetic energy distributions of the photodissociation fragments contain detailed information about the final state of N2+. Comparison with data for N+ photodesorption and electron yield data for condensed N2 indicates that the desorption signal is dominated by an essentially purely repulsive final state of N2+.