Quantum Dynamics Simulation of the Ultrafast Photoionization of Li2

Published

January 1, 2001

Author(s)

J Pesce, Z Amitay, R Uberna, S R. Leone, M Ratner, R Kosloff

Abstract

The Li₂ species offers an ideal system to compare experimental pump/probe ultrafast photoionization with quantum dynamical calculations on well characterized potential energy surfaces. The present work utilizes the best available potential energy surfaces and appropriate quantum dynamical methods to analyze the photoionization and dynamics of a wave packet prepared in the E ¹ς⁺_g shelf state of lithium dimer. A direct comparison between calculated (ab initio) and measured quantum dynamics is made for signals obtained with different laser pulse shapes, intensities, and chirps, and the validity of the theoretical model is considered, as well as the applicability and failure of perturbation theory. The results illustrate the high sensitivity of the time-dependent pump/probe ionization transient signals to the detailed modeling of both the pump and probe stages. They also show some of the inadequacies of the current potential surfaces and dipole moment matrix elements of lithium dimer.

Citation

Journal of Chemical Physics

Volume

114

Issue

No. 3

Pub Type

Journals

Keywords

Li₂, lithium dimer, theory, ultrafast photoionization

Citation

Pesce, J. , Amitay, Z. , Uberna, R. , Leone, S. , Ratner, M. and Kosloff, R. (2001), Quantum Dynamics Simulation of the Ultrafast Photoionization of Li₂, Journal of Chemical Physics (Accessed October 22, 2025)