Implementation of the CCSD-PCM linear response function for frequency dependent properties in solution: Application to polarizability and specific rotation
Implementation of the CCSD-PCM linear response function for frequency dependent properties in solution: Application to polarizability and specific rotation
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DOI：
10.1063/1.4821087
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发表时间：
2013-09-21
影响因子：
4.4
通讯作者：
Caricato, Marco
中科院分区：
文献类型：
--
作者：
Caricato, Marco
本工作报告的频率依赖的线性响应（LR）功能的耦合集群单打和双打的方法（CCSD）结合极化连续模型的溶剂化溶液中的频率依赖性的计算功能的第一次实施。特别是，静态和动态极化率以及比旋光度的值，提出了各种测试分子。极化率的模型计算表明，一个共同的近似使用的LR函数的定义与溶剂化模型恢复超过70%的完整的响应，同时保持计算成本相媲美的气相LR-CCSD。三种化合物的气相方法预测旋转的错误符号的比旋计算表明，占溶剂的电子响应可能是必不可少的分配正确的绝对构型的手性分子。(C)2013 AIP Publishing LLC.
This work reports the first implementation of the frequency dependent linear response (LR) function for the coupled cluster singles and doubles method (CCSD) combined with the polarizable continuum model of solvation for the calculation of frequency dependent properties in solution. In particular, values of static and dynamic polarizability as well as specific rotation are presented for various test molecules. Model calculations of polarizability show that a common approximation used in the definition of the LR function with solvation models recovers over 70% of the full response while maintaining a computational cost comparable to gas phase LR-CCSD. Calculations of specific rotation for three compounds for which gas phase methods predict the wrong sign of the rotation show that accounting for the electronic response of the solvent may be essential to assign the correct absolute configuration of chiral molecules. (C) 2013 AIP Publishing LLC.