Effects of Autoionizing Resonances on Wave-Packet Dynamics Studied by Time-Resolved Photoelectron Spectroscopy.

Abstract

We report a combined experimental and theoretical study on the effect of autoionizing resonances in time-resolved photoelectron spectroscopy. The coherent excitation of N_{2} by ∼14.15 eV extreme-ultraviolet photons prepares a superposition of three dominant adjacent vibrational levels (v^{'}=14-16) in the valence b^{'} ^{1}Σ_{u}^{+} state, which are probed by the absorption of two or three near-infrared photons (800nm). The superposition manifests itself as coherent oscillations in the measured photoelectron spectra. A quantum-mechanical simulation confirms that two autoionizing Rydberg states converging to the excited A ^{2}Π_{u} and B ^{2}Σ_{u}^{+} N_{2}^{+} cores are accessed by the resonant absorption of near-infrared photons. We show that these resonances apply different filters to the observation of the vibrational wave packet, which results in different phases and amplitudes of the oscillating photoelectron signal depending on the nature of the autoionizing resonance. This work clarifies the importance of resonances in time-resolved photoelectron spectroscopy and particularly reveals the phase of vibrational quantum beats as a powerful observable for characterizing the properties of such resonances.