Ultrafast dissociation of ammonia: Auger Doppler effect and redistribution of the internal energy

Abstract

We study vibrationally-resolved resonant Auger (RAS) spectra of ammonia recorded in coincidence with the NH₂⁺ fragment, which is produced in the course of dissociation either in the core-excited 1s⁻¹4a¹₁ intermediate state or the first spectator 3a⁻²4a¹₁ final state. Correlation of the NH₂⁺ ion flight times with electron kinetic energies allows directly observing the Auger-Doppler dispersion for each vibrational state of the fragment. The median distribution of the kinetic energy release E_KER, derived from the coincidence data, shows three distinct branches as a function of Auger electron kinetic energy E_e: E_e + 1.75E_KER = const for the molecular band; E_KER = const for the fragment band; and E_e + E_KER = const for the region preceding the fragment band. The deviation of the molecular band dispersion from E_e + E_KER = const is attributed to the redistribution of the available energy to the dissociation energy and excitation of the internal degrees of freedom in the molecular fragment. We found that for each vibrational line the dispersive behavior of E_KERvs. E_e is very sensitive to the instrumental uncertainty in the determination of E_KER causing the competition between the Raman (E_KER + E_e = const) and Auger (E_e = const) dispersions: increase in the broadening of the finite kinetic energy release resolution leads to a change of the dispersion from the Raman to the Auger one.