Temporary Anion States of Ethene Interacting with Single Molecules of Methane, Ethane, and Water
Temporary Anion States of Ethene Interacting with Single Molecules of Methane, Ethane, and Water
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乙烯与甲烷、乙烷和水单分子相互作用的临时阴离子态
DOI：
10.1021/acs.jpca.7b12669
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
M. Ehara
中科院分区：
文献类型：
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作者：
T. Sommerfeld;J. B. Melugin;M. Ehara
当一个多余的电子被加到乙烯的π* 轨道上时，所产生的阴离子通过电子自动脱离而衰变;也就是说，它代表一种被称为暂时阴离子或共振态的电子状态。在这里，集群环境的能量和寿命的这种状态的影响进行了研究。所考虑的簇是乙烯···CH 4、乙烯···C2 H6和乙烯···H2O。这些簇中的大多数被系统地构造，使得溶剂以特定的方式与π系统相互作用，因此通过构造，相对于所有分子间自由度不是最小的。然而，对于水，此外，一个最小的能量结构进行检查。系统的溶剂和溶剂化几何形状的变化，使我们能够确定由于极化率，排除体积，和极性的溶剂分子的影响的趋势。采用自适应的团簇构型相互作用电子结构方法结合复吸收势计算了乙烯和所有临时团簇阴离子的共振参数。该方法对于小至中等大小的分子是公认的。除了溶剂化效应本身的研究，有多少个基础功能需要对封闭壳溶剂化单元的问题进行检查。
When an excess electron is added into the π* orbital of ethene, the resulting anion decays by electron autodetachment; that is, it represents an electronic state referred to as a temporary anion or resonance state. Here, the influence of a cluster environment on the energy and lifetime of this state is investigated. The clusters considered are ethene···CH4, ethene···C2H6, and ethene···H2O. Most of these clusters are systematically constructed so that the solvent interacts with the π system in a specific way, and are thus by construction not minima with respect to all intermolecular degrees of freedom. However, for water, in addition, a minimal energy structure is examined. Systematic variation of the solvent and solvation geometry allows us to identify trends regarding effects due to polarizability, excluded volume, and polarity of the solvent molecules. The resonance parameters of ethene and all temporary cluster anions are computed with the symmetry-adapted cluster-configuration interaction electronic structure method in combination with a complex absorbing potential. This method is well-established for small to intermediate sized molecules. In addition to the study of the solvation effects themselves, the question of how many basis functions are needed on the closed-shell solvating unit is examined.