Reactivity of an excess electron with monovalent cations in bulk water by mixed quantum classical molecular dynamics simulations

被引:3
作者
Spezia, R
Nicolas, C
Coudert, FX
Archirel, P
Vuilleumier, R
Boutin, A [1 ]
机构
[1] Univ Paris 11, Chim Phys Lab, CNRS, UMR 8000, F-91405 Orsay, France
[2] Univ Rome, Dipartimento Chim, Rome, Italy
[3] Univ Paris 06, Phys Theor Liquides Lab, CNRS, UMR 7600, F-75252 Paris 05, France
关键词
molecular dynamics; silver cation; absorption spectra; thermodynamic cycle;
D O I
10.1080/0892702042000270142
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
A mixed quantum classical molecular dynamics (QCMD) simulation of the silver and sodium cations in presence of an excess electron is reported. The silver cation is shown to be reduced by the hydrated electron and to form a stable, highly polarized, neutral atom. On the contrary the sodium cation is not reduced and a metastable contact ion pair is observed. The resulting absorption spectra of both species are compared with experiments and shown to be in good agreement. Furthermore, the free energy curve for the charge separation was calculated and rationalized in terms of a thermodynamic cycle. Finally, a direct, reactive, molecular dynamics trajectory provides some useful informations on the reduction mechanism.
引用
收藏
页码:749 / 754
页数:6
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