Hršak Dalibor, Olsen Jógvan Magnus Haugaard, Kongsted Jacob
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, Odense M, 5230, Denmark.
J Comput Chem. 2017 Sep 15;38(24):2108-2117. doi: 10.1002/jcc.24859. Epub 2017 Jun 22.
Embedding techniques in combination with response theory represent a successful approach to calculate molecular properties and excited states in large molecular systems such as solutions and proteins. Recently, the polarizable embedding model has been extended by introducing explicit electronic densities of the molecules in the nearest environment, resulting in the polarizable density embedding (PDE) model. This improvement provides a better description of the intermolecular interactions at short distances. However, the electronic densities of the environment molecules are calculated in isolation, which results in overestimation of the non-electrostatic repulsion, thereby requiring a scaling of this term. In this work, an optimal scaling factor for the non-electrostatic repulsion term is examined by comparing intermolecular interaction energies obtained with embedding techniques to reference interaction energies calculated on the basis of full quantum-mechanical calculations. The obtained optimal factors are used in PDE calculations of various ground- and excited-state properties of molecules embedded in solvents described as polarizable environments. © 2017 Wiley Periodicals, Inc.
嵌入技术与响应理论相结合是一种成功的方法，可用于计算大分子体系（如溶液和蛋白质）的分子性质和激发态。最近，通过引入最近环境中分子的显式电子密度，可极化嵌入模型得到了扩展，从而产生了可极化密度嵌入（PDE）模型。这一改进能更好地描述短距离内的分子间相互作用。然而，环境分子的电子密度是孤立计算的，这导致非静电排斥的高估，因此需要对该项进行缩放。在这项工作中，通过将嵌入技术获得的分子间相互作用能与基于全量子力学计算得到的参考相互作用能进行比较，研究了非静电排斥项的最佳缩放因子。所获得的最佳因子用于对嵌入可极化环境溶剂中的分子的各种基态和激发态性质进行PDE计算。© 2017威利期刊公司。
