ULTRAFAST ELECTRONIC RELAXATION DYNAMICS - A COMPARISON BETWEEN WATER AND IONIC AQUEOUS-SOLUTIONS

被引:24
作者
GAUDUEL, Y
GELABERT, H
ASHOKKUMAR, M
机构
[1] Laboratoire d'Optique Appliquée, CNRS URA 1406, INSERM U275 Ecole Polytechnique - ENS Techniques Avancées
关键词
D O I
10.1016/0167-7322(95)92821-R
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Femtosecond spectroscopy of aqueous solutions at room temperature allows to investigate electronic dynamics triggered by the energy deposition and a subsequent excess electron photodetachment from solvent or solute (chloride ion). In ionic aqueous solutions, early physicochemical processes are analyzed within the frequency domain 27 10(3) - 7.7 10(3) cm(-1) by considering multiple time-resolved electronic relaxation channels: electron localization within the solvation shells of chlorine atom, electron-ion pair formation, deactivation of excited charge transfer to solvent states (excited CTTS states). At short time (0.5 ps < t < 4ps) ultrafast electron-chlorine atom recombination reaction (k(A) similar to 3 10(12) S-1) competes with a second electron hydration channel (k(B) - 1.3 10(12) s(-1)). The direct characterization of ultrafast electron-atom reactions in polar solutions provide further basis for(i)) the investigation of ultrashort-lived solvent cage effects at the microscopic level, (ii))) a better understanding of quantum branching processes during ultrafast electron transfer reactions, (iii)) a knowledge on the role of reorientational correlation function of solvent molecules around semi-ionized and metastable electronic states.
引用
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页码:57 / 71
页数:15
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