Hydrated electron dynamics: From clusters to bulk

被引:236
作者
Bragg, AE
Verlet, JRR
Kammrath, A
Cheshnovsky, O
Neumark, DM [1 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] Tel Aviv Univ, Sackler Fac Exact Sci, Sch Chem, IL-69978 Tel Aviv, Israel
[3] Univ Calif Berkeley, Lawrence Berkeley Lab, Div Chem Sci, Berkeley, CA 94720 USA
关键词
D O I
10.1126/science.1103527
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
The electronic relaxation dynamics of size-selected (H2O)(n)(-)/(D2O)(n)(-)[25less than or equal tonless than or equal to50] clusters have been studied with time-resolved photoelectron imaging. The excess electron (e(c)(-)) was excited through the e(c)(-)(p)<--e(c)(-)(s) transition with an ultrafast laser pulse, with subsequent evolution of the excited state monitored with photodetachment and photoelectron imaging. All clusters exhibited p-state population decay with concomitant s-state repopulation (internal conversion) on time scales ranging from 180 to 130 femtoseconds for (H2O)n- and 400 to 225 femtoseconds for (D2O)(n)(-); the lifetimes decrease with increasing cluster sizes. Our results support the "nonadiabatic relaxation" mechanism for the bulk hydrated electron (e(aq)(-)), which invokes a 50-femtosecond e(aq)(-) (p)-->e(aq)(-) (s(dagger)) internal conversion lifetime.
引用
收藏
页码:669 / 671
页数:3
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