Extended polarization in third-order SCC-DFTB from chemical-potential equalization.
Extended polarization in third-order SCC-DFTB from chemical-potential equalization.
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DOI：
10.1021/jp306239c
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发表时间：
2012-09-13
影响因子：
2.9
通讯作者：
Elstner, Marcus
中科院分区：
文献类型：
--
作者：
Kaminski, Steve;Giese, Timothy J.;Gaus, Michael;York, Darrin M.;Elstner, Marcus
在本工作中，我们增加了近似密度泛函方法SCC-DFTB（DFTB 3）与化学势平衡（CPE）的方法，以提高性能的分子的电子极化率。CPE方法最初是Giese和约克为NDDO类方法实现的，现已被证明对最小基方法的响应性质有显著的修正，最近已被应用于SCC-DFTB。CPE可以通过提供额外的响应密度来克服最小基方法的固有限制。因此，在不需要扩展原子轨道基础的情况下，即在不显著增加总体计算成本的情况下，定量地校正系统低估。特别是作为分子电荷状态的函数的极化率的依赖性从DFTB 3的CPE扩展显著改善。引入的CPE方法的经验参数进行了优化，为172个有机分子，以匹配的结果从密度泛函方法（DFT）方法，使用大基组。然而，分子极化率的一阶导数（例如计算拉曼活性所需的）没有通过当前CPE实现得到改善，即，拉曼光谱没有得到改善。
In this work we augment the approximate density functional method SCC-DFTB (DFTB3) with the chemical potential equilization (CPE) approach in order to improve the performance for molecular electronic polarizabilities. The CPE method, originally implemented for NDDO type methods by Giese and York, has been shown to emend minimal basis methods wrt response properties significantly, and has been applied to SCC-DFTB recently. CPE allows to overcome this inherent limitation of minimal basis methods by supplying an additional response density. The systematic underestimation is thereby corrected quantitatively without the need to extend the atomic orbital basis, i.e. without increasing the overall computational cost significantly. Especially the dependency of polarizability as a function of molecular charge state was significantly improved from the CPE extension of DFTB3. The empirical parameters introduced by the CPE approach were optimized for 172 organic molecules in order to match the results from density functional methods (DFT) methods using large basis sets. However, the first order derivatives of molecular polarizabilities, as e.g. required to compute Raman activities, are not improved by the current CPE implementation, i.e. Raman spectra are not improved.
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DOI：
10.1007/bf00548085
发表时间：
1977-01-01
期刊：
THEORETICA CHIMICA ACTA
影响因子：
--
作者：
DEWAR, MJS;THIEL, W
通讯作者：
THIEL, W
影响因子：
--
作者：
Hueckel, Erich
通讯作者：
Hueckel, Erich
影响因子：
3
作者：
KOLB, M;THIEL, W
通讯作者：
THIEL, W
影响因子：
--
作者：
MATSUZAWA, N;DIXON, DA
通讯作者：
DIXON, DA
影响因子：
5.5
作者：
Gaus, Michael;Cui, Qiang;Elstner, Marcus
通讯作者：
Elstner, Marcus