Caprasecca Stefano, Jurinovich Sandro, Viani Lucas, Curutchet Carles, Mennucci Benedetta
Dipartimento di Chimica e Chimica Industriale, University of Pisa , Via Risorgimento 35, 56126 Pisa, Italy.
Departament de Fisicoquímica Facultat de Farmàcia, Universitat de Barcelona Av. Joan XXIII s/n, 08028 Barcelona, Spain.
J Chem Theory Comput. 2014 Apr 8;10(4):1588-98. doi: 10.1021/ct500021d.
We present the mathematical derivation and the computational implementation of the analytical geometry derivatives for a polarizable QM/MM model (QM/MMPol). In the adopted QM/MMPol model, the focused part is treated at QM level of theory, while the remaining part (the environment) is described classically as a set of fixed charges and induced dipoles. The implementation is performed within the ONIOM procedure, resulting in a polarizable embedding scheme, which can be applied to solvated and embedded systems and combined with different polarizable force fields available in the literature. Two test cases characterized by strong hydrogen-bond and dipole-dipole interactions, respectively, are used to validate the method with respect to the nonpolarizable one. Finally, an application to geometry optimization of the chromophore of Rhodopsin is presented to investigate the impact of including mutual polarization between the QM and the classical parts in conjugated systems.
我们给出了可极化量子力学/分子力学模型（QM/MMPol）的解析几何导数的数学推导和计算实现。在所采用的QM/MMPol模型中，聚焦部分采用量子力学理论水平进行处理，而其余部分（环境）则经典地描述为一组固定电荷和诱导偶极子。该实现是在ONIOM程序中进行的，从而得到一种可极化嵌入方案，该方案可应用于溶剂化和嵌入系统，并可与文献中可用的不同可极化力场相结合。分别以强氢键和偶极 - 偶极相互作用为特征的两个测试案例被用于验证该方法相对于非极化方法的性能。最后，给出了对视紫红质发色团几何优化的应用，以研究在共轭体系中包含量子力学部分和经典部分之间相互极化的影响。
