title: Predissociation dynamics of lithium iodide.
abstract: The predissociation dynamics of lithium iodide (LiI) in the first excited A-state is investigated for molecules in the gas phase and embedded in helium nanodroplets, using femtosecond pump-probe photoionization spectroscopy. In the gas phase, the transient Li(+) and LiI(+) ion signals feature damped oscillations due to the excitation and decay of a vibrational wave packet. Based on high-level ab initio calculations of the electronic structure of LiI and simulations of the wave packet dynamics, the exponential signal decay is found to result from predissociation predominantly at the lowest avoided X-A potential curve crossing, for which we infer a coupling constant VXA = 650(20) cm(-1). The lack of a pump-probe delay dependence for the case of LiI embedded in helium nanodroplets indicates fast droplet-induced relaxation of the vibrational excitation.
authors: Physikalisches Institut, Universität Freiburg, 79104 Freiburg, Germany.
authors: H
authors: H
authors: Schmidt
authors: Physikalisches Institut, Universität Freiburg, 79104 Freiburg, Germany.
authors: J
authors: J
authors: von Vangerow
authors: Physikalisches Institut, Universität Freiburg, 79104 Freiburg, Germany.
authors: F
authors: F
authors: Stienkemeier
authors: Institute of Chemical Kinetics and Combustion, Novosibirsk 630090, Russia.
authors: A S
authors: AS
authors: Bogomolov
authors: Institute of Chemical Kinetics and Combustion, Novosibirsk 630090, Russia.
authors: A V
authors: AV
authors: Baklanov
authors: Theoretische Physik, Universität Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, Germany.
authors: D M
authors: DM
authors: Reich
authors: Theoretische Physik, Universität Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, Germany.
authors: W
authors: W
authors: Skomorowski
authors: Theoretische Physik, Universität Kassel, Heinrich-Plett-Str. 40, 34132 Kassel, Germany.
authors: C P
authors: CP
authors: Koch
authors: Physikalisches Institut, Universität Freiburg, 79104 Freiburg, Germany.
authors: M
authors: M
authors: Mudrich