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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{sup +} and LiI{sup +} 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 V{sub XA} = 650(20) cm{sup −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:
; ; ;  [1];  [2];  [2];  [3]; ; ;  [4]
  1. Physikalisches Institut, Universität Freiburg, 79104 Freiburg (Germany)
  2. Institute of Chemical Kinetics and Combustion, Novosibirsk 630090 (Russian Federation)
  3. (Russian Federation)
  4. Theoretische Physik, Universität Kassel, Heinrich-Plett-Str. 40, 34132 Kassel (Germany)
Publication Date:
OSTI Identifier:
22416047
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COUPLING CONSTANTS; DIAGRAMS; DROPLETS; ELECTRONIC STRUCTURE; EXCITATION; HELIUM; LITHIUM IODIDES; LITHIUM IONS; MOLECULES; OSCILLATIONS; PHOTOIONIZATION; POTENTIALS; PREDISSOCIATION; PROBES; RELAXATION; WAVE PACKETS

Citation Formats

Schmidt, H., Vangerow, J. von, Stienkemeier, F., Mudrich, M., E-mail: mudrich@physik.uni-freiburg.de, Bogomolov, A. S., Baklanov, A. V., Novosibirsk State University, Novosibirsk 630090, Reich, D. M., Skomorowski, W., and Koch, C. P. Predissociation dynamics of lithium iodide. United States: N. p., 2015. Web. doi:10.1063/1.4906512.
Schmidt, H., Vangerow, J. von, Stienkemeier, F., Mudrich, M., E-mail: mudrich@physik.uni-freiburg.de, Bogomolov, A. S., Baklanov, A. V., Novosibirsk State University, Novosibirsk 630090, Reich, D. M., Skomorowski, W., & Koch, C. P. Predissociation dynamics of lithium iodide. United States. doi:10.1063/1.4906512.
Schmidt, H., Vangerow, J. von, Stienkemeier, F., Mudrich, M., E-mail: mudrich@physik.uni-freiburg.de, Bogomolov, A. S., Baklanov, A. V., Novosibirsk State University, Novosibirsk 630090, Reich, D. M., Skomorowski, W., and Koch, C. P. Wed . "Predissociation dynamics of lithium iodide". United States. doi:10.1063/1.4906512.
@article{osti_22416047,
title = {Predissociation dynamics of lithium iodide},
author = {Schmidt, H. and Vangerow, J. von and Stienkemeier, F. and Mudrich, M., E-mail: mudrich@physik.uni-freiburg.de and Bogomolov, A. S. and Baklanov, A. V. and Novosibirsk State University, Novosibirsk 630090 and Reich, D. M. and Skomorowski, W. and Koch, C. P.},
abstractNote = {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{sup +} and LiI{sup +} 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 V{sub XA} = 650(20) cm{sup −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.},
doi = {10.1063/1.4906512},
journal = {Journal of Chemical Physics},
number = 4,
volume = 142,
place = {United States},
year = {Wed Jan 28 00:00:00 EST 2015},
month = {Wed Jan 28 00:00:00 EST 2015}
}