Highest electron affinity as a predictor of cluster anion structures

被引:68
作者
Kronik, L
Fromherz, R
Ko, E
Ganteför, G
Chelikowsky, JR [1 ]
机构
[1] Univ Minnesota, Dept Chem Engn & Mat Sci, Minneapolis, MN 55455 USA
[2] Univ Minnesota, Minnesota Supercomp Inst, Minneapolis, MN 55455 USA
[3] Univ Konstanz, Dept Phys, D-78457 Constance, Germany
基金
美国国家科学基金会;
关键词
D O I
10.1038/nmat704
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
Small clusters have a range of unique physical and chemical phenomena that are strongly size dependent. However, analysis of these phenomena often assumes that thermodynamic equilibrium conditions prevail. We compare experimentally measured and ab initio computed photoelectron spectra of bare and deuterated silicon cluster anions produced in a plasma environment. We find that the isomers detected experimentally are usually not the ground-state isomers, but metastable ones, which indicates that cluster relaxation is strongly limited kinetically by a dwell time that is much shorter than the relaxation time. We show that, under these conditions, the highest electron affinity replaces the traditional lowest total energy as the appropriate criterion for predicting isomer structures. These findings demonstrate that a stringent examination of non-equilibrium effects can be crucial for a correct analysis of cluster properties.
引用
收藏
页码:49 / 53
页数:5
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