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Femtosecond Relaxation Dynamics of Solvated Electrons in Liquid Ammonia
Author(s) -
Lindner Jörg,
Unterreiner AndreasN.,
Vöhringer Peter
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200500467
Subject(s) - photoexcitation , solvated electron , femtosecond , relaxation (psychology) , absorption spectroscopy , chemistry , spectroscopy , electron , chemical physics , absorption (acoustics) , ultrafast laser spectroscopy , ultrashort pulse , atomic physics , molecular physics , laser , excited state , optics , physics , psychology , social psychology , radiolysis , quantum mechanics , aqueous solution
10.1002/cphc.200500467.abs The ultrafast relaxation dynamics of the well‐known solvated electron in liquid ammonia solutions are investigated with femtosecond near‐infrared pump–probe absorption spectroscopy. Immediately after photoexcitation, the dynamic absorption spectrum of the electron is substantially red‐shifted with respect to its stationary spectrum. A subsequent dynamic blue shift of the pump–probe spectrum occurs on a timescale of 150 fs. The data are understood in terms of ground‐state “cooling” and can be quantitatively simulated by an intuitive temperature‐jump model employing a dynamically evolving Kubo line shape for the electronic resonance. A simple estimate implies that, on average, the electron in the liquid is coordinated to six nearest‐neighbor ammonia molecules. An equivalent analysis of the data based on a bubble‐formation/cavity‐contraction mechanism is briefly outlined.