Combining frozen‐density embedding with the conductor‐like screening model using Lagrangian techniques for response properties
Combining frozen‐density embedding with the conductor‐like screening model using Lagrangian techniques for response properties
复制标题
使用拉格朗日技术将冻结密度嵌入与类导体筛选模型相结合以获得响应特性
DOI：
10.1002/jcc.24813
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发表时间：
2017
影响因子：
3
通讯作者：
S. Höfener
中科院分区：
文献类型：
--
作者：
Nils Schieschke;Roberto Di Remigio;L. Frediani;J. Heuser;S. Höfener
我们提出了一种在复杂环境中对分子进行多尺度描述的方法，该方法将冻结密度嵌入（FDE）与连续溶剂化模型，特别是导体屏蔽模型（COSMO）相结合。FDE以降低的计算成本提供了分子-环境相互作用的显式原子描述，而外部连续层则考虑了长程各向同性静电相互作用的影响。我们的处理是基于变分拉格朗日框架，使地面和激发态响应特性的严格推导。作为理论框架灵活性的一个例子，我们推导并讨论了在Tamm-Dancoff近似（TDA）下激发态的FDE + COSMO分析分子梯度，以及在二阶Møller-Plesset微扰理论（MP2）和二阶近似耦合团簇（CC 2）下基态的FDE + COSMO分析分子梯度。它示出了如何使用这种方法来描述垂直电子激发（VEE）能量和斯托克斯位移尿嘧啶在水中和喹诺酮在二甲基亚砜（DMSO），分别。此外，一些简化的蛋白质模型的VEE计算，说明该方法的性能时，应用到更大的系统。FDE子系统密度和连续体之间的相互作用项可以影响高达0.3 eV的激发能量，因此，对于一般应用来说，不能忽略。我们发现，净影响的连续存在的第一FDE壳上的激发能量约为0.05 eV的情况下调查。目前的工作是一个重要的一步，严格推导从头算多层和多尺度建模方法。© 2017 Wiley Periodicals，Inc.
We present the explicit derivation of an approach to the multiscale description of molecules in complex environments that combines frozen‐density embedding (FDE) with continuum solvation models, in particular the conductor‐like screening model (COSMO). FDE provides an explicit atomistic description of molecule‐environment interactions at reduced computational cost, while the outer continuum layer accounts for the effect of long‐range isotropic electrostatic interactions. Our treatment is based on a variational Lagrangian framework, enabling rigorous derivations of ground‐ and excited‐state response properties. As an example of the flexibility of the theoretical framework, we derive and discuss FDE + COSMO analytical molecular gradients for excited states within the Tamm–Dancoff approximation (TDA) and for ground states within second‐order Møller–Plesset perturbation theory (MP2) and a second‐order approximate coupled cluster with singles and doubles (CC2). It is shown how this method can be used to describe vertical electronic excitation (VEE) energies and Stokes shifts for uracil in water and carbostyril in dimethyl sulfoxide (DMSO), respectively. In addition, VEEs for some simplified protein models are computed, illustrating the performance of this method when applied to larger systems. The interaction terms between the FDE subsystem densities and the continuum can influence excitation energies up to 0.3 eV and, thus, cannot be neglected for general applications. We find that the net influence of the continuum in presence of the first FDE shell on the excitation energy amounts to about 0.05 eV for the cases investigated. The present work is an important step toward rigorously derived ab initio multilayer and multiscale modeling approaches. © 2017 Wiley Periodicals, Inc.
DOI：
10.1016/s0167-4838(98)00100-9
发表时间：
1998-08
期刊：
Biochimica et biophysica acta
影响因子：
--
作者：
Monique Laberge
通讯作者：
Monique Laberge