A polarizable embedding approach to second harmonic generation (SHG) of molecular systems in aqueous solutions
A polarizable embedding approach to second harmonic generation (SHG) of molecular systems in aqueous solutions
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DOI：
10.1007/s00214-018-2247-7
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发表时间：
2018-05-07
影响因子：
1.7
通讯作者：
Cappelli, Chiara
中科院分区：
文献类型：
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作者：
Giovannini, Tommaso;Ambrosetti, Matteo;Cappelli, Chiara
我们给出了原子全极化QM/FQ方法的二次谐波产生(SHG)的扩展，该方法原子化地处理溶剂，并在溶剂中嵌入一个波动电荷(FQ)，该电荷以自洽的方式响应于溶质量子力学(QM)静电势。所提出的方法能够在量子力学响应方程和体系构象性质上实现对溶剂效应的充分模拟，并借助于分子动力学模拟进行采样。将该模型应用于水溶液中与周围环境的相互作用以HB相互作用为主的部分有机酸，无论是对溶剂效应的模拟，还是对从超拉曼散射实验中提取的实验倍频数据的再现，都显示出很好的一致性。
We present the extension to second harmonic generation (SHG) of the atomistic fully polarizable QM/FQ method that treats the solvent atomistically and embeds each atom in the solvent with a fluctuating charge (FQ) which responds to the solute quantum mechanical (QM) electrostatic potential in a self-consistent manner. The proposed approach is able to achieve an adequate modeling of solvent effects both in the quantum mechanical response equations and on the conformational properties of the system, which is sampled by resorting to molecular dynamics simulations. The application of the model to selected organic acids in aqueous solution, for which the interaction with the surrounding environment is dominated by HB interactions, shows a good agreement in both the modeling of solvent effects and in the reproduction of experimental SHG data extracted from hyper-Raman scattering experiments.