First-principles calculation of local atomic polarizabilities.
First-principles calculation of local atomic polarizabilities.
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DOI：
10.1021/jp073151y
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发表时间：
2007-10
期刊：
影响因子：
--
通讯作者：
Timothy C. Lillestolen;R. Wheatley
中科院分区：
文献类型：
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作者：
Timothy C. Lillestolen;R. Wheatley
确定原子极化率的常用方法会受到非局部效应（例如电荷极化）的影响。描述了一种基于计算原子多极对局部静电势的响应来完全从头开始确定原子极化率的新方法。然后使用局部原子极化率来计算感应能，并将其与从头计算感应能进行比较，以测试它们在实际应用中的有用性。这些极化率在绝对精度和多极感应级数的收敛性方面均优于相应的分子极化率。还讨论了烷烃系列的局域极化率的可传递性。
Common methods of determining atomic polarizabilities suffer from the inclusion of nonlocal effects such as charge polarization. A new method is described for determining fully ab initio atomic polarizabilities based on calculating the response of atomic multipoles to the local electrostatic potential. The localized atomic polarizabilities are then used to calculate induction energies that are compared to ab initio induction energies to test their usefulness in practical applications. These polarizabilities are shown to be an improvement over the corresponding molecular polarizabilities, in terms of both absolute accuracy and the convergence of the multipolar induction series. The transferability of localized polarizabilities for the alkane series is also discussed.