Ab initio molecular dynamics simulation of a medium-sized water cluster anion:: From an interior to a surface-located excess electron via a delocalized state
Ab initio molecular dynamics simulation of a medium-sized water cluster anion:: From an interior to a surface-located excess electron via a delocalized state
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DOI：
10.1021/jp711545s
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发表时间：
2008-07-10
影响因子：
2.9
通讯作者：
Jungwirth, Pavel
中科院分区：
文献类型：
--
作者：
Frigato, Tomaso;VandeVondele, Joost;Jungwirth, Pavel
我们提出了一个计算研究的结构和动力学的一个多余的电子在一个中等大小的水团簇，旨在解决内部与外部溶剂化的问题。在DFT框架内进行了从头算Born-Oppenheimer分子动力学模拟，采用混合高斯和平面波形式主义与PBE交换相关泛函和范数守恒赝势。15 ps轨迹的分析使我们能够得出以下结论：（i）多余的电子主要位于团簇表面（即使它最初被放置在内部），（ii）计算的电子结合能与电子本地化，而不是与它的体积与表面位置，和（iii）之间的动态相互转换两个不同的氢键模式的电子周围发生。计算的电子结合能和瓷砖的红外光谱的最相关的功能是在一个非常好的协议与以前的实验研究结果。
We present a computational study of the structure and dynamics of an excess electron in a medium-sized water cluster aimed at addressing the question of interior vs exterior solvation. Ab initio Born - Oppenheimer molecular dynamics simulations were performed within the DFT framework, employing a hybrid Gaussian and plane-wave formalism together with the PBE exchange-correlation functional and norm-conserving pseudopotentials. Analysis of a 15-ps trajectory allowed us to reach the following conclusions: (i) the excess electron is predominantly located at the cluster surface (even if it is initially placed in the interior), (ii) the computed electron binding energies correlate with the electron localization rather than with its bulk vs surface location, and (iii) a dynamical interconversion between two different H-bond patterns around the electron occurs. The computed electron binding energies and tile most relevant features of the IR spectrum are in a very good agreement with results of previous experimental studies.