Electronic structural basis for the atomic partial charges of planar molecular systems derived from out-of-plane dipole derivatives
Electronic structural basis for the atomic partial charges of planar molecular systems derived from out-of-plane dipole derivatives
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面外偶极子导数平面分子系统原子部分电荷的电子结构基础
DOI：
10.1021/jp512884g
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发表时间：
2015
期刊：
影响因子：
2.9
通讯作者：
H. Torii
中科院分区：
文献类型：
--
作者：
畑昌育，坂上仁志，城崎知至，千徳靖彦，長友 英夫;H. Torii and S. Noge;H. Torii;佐藤竜馬，坂上仁志，砂原淳，城崎知至，長友英夫;H. Torii
从面外偶极导数推导原子部分电荷的方法作为一种确定分子运动时电荷分布变化的有用方法，重新引起了人们的兴趣。为了了解这些原子部分电荷的性质并探索该方法可能的广泛适用性，通过计算二维电子极化导数，分析了平面外原子位移引起的电子密度调制。结果表明，它们的振幅基本上离域到邻近原子的空间区域，这表明将该方法应用于局部平面系统所需的平面区域的大小，例如由烷基覆盖的肽基。在分子配合物中，电子极化导数的振幅受极化效应的影响较大，这为利用该方法估计氢键体系中分子间电荷转移的程度提供了方法。
The method of deriving atomic partial charges from out-of-plane dipole derivatives has gained renewed interest as a useful method for identifying the changes in charge distribution upon molecular motion. To understand the nature of those atomic partial charges and to explore possible wide applicability of this method, the modulations in the electron density induced by out-of-plane atomic displacements are analyzed by calculating two-dimensional electronic polarization derivatives. It is shown that their amplitudes are substantially delocalized to the spatial regions of the adjacent atoms, suggesting the size of the planar region required for applying this method tolocallyplanar systems, such as the peptide group capped by alkyl groups. It is also shown that, in molecular complexes, the amplitudes of electronic polarization derivatives are affected rather strongly by the polarization effect, indicating the way to use this method to estimate the extent of intermolecular charge transfer in hydrogen-bonded systems.