Time-resolved photoelectron spectroscopy of molecular dissociation: Classical trajectory versus quantum wave-packet calculations

Abstract

We present a simulation of ultrafast pump-probe photoelectron spectroscopy based on a classical treatment of the nuclear motion. A comparison with quantum mechanical wave-packet results shows that in the case of the direct dissociation of H 2 O in its A ˜1B 1 electronic state this method produces extremely accurate results. The energy distribution of the photoelectrons recorded as a function of the pump-probe delay reflects the dissociation process, which takes place within only a few femtoseconds.

Quantum dynamics of solid Ne upon photo-excitation of a NO impurity: A Gaussian wave packet approach

“…The measured signal is the C and D states fluorescence recorded as a function of the delay time between the two pulses. For pulses that are short compared with the system dynamics, the measured signal can be described within the impulsive limit by 58,59 …”

Femtosecond Time‐Resolved Photoelectron Spectroscopy

“…Due to the differing energy phase factors of the eigenstates, this superposition is nonstationary. Extensive theoretical treatment of the propagation and probing of nonstationary states in a TRPES experiment may be found elsewhere; [26][27][28][29][30][31][32] only a descriptive summary of the theory follows.…”

“…31 The authors calculated that, witha6fsVUVpump pulse at 155 nm, the dissociation dynamics of H 2 O( Ã 1 B 1 ) is revealed directly by TRPES, usinga6f sX U Vprobe pulse at 86.7 nm (14.3 eV). As the H atom separated from OH, the photoelectron spectra shifted, in 10-20 fs, from a broad peak at 0.4 eV to a sharper peak at 0.1 eV.…”

High-harmonic transient grating spectroscopy of NO2 electronic relaxation

“…The starting point in the phase space and the starting time of the trajectories are obtained by applying the classical treatment proposed by Meier and Engel 44 . The initial phase space distribution is obtained by a two-step procedure.…”