Modeling Complex Solvent Effects on the Optical Rotation of Chiral Molecules: A Combined Molecular Dynamics and Density Functional Theory Study
Modeling Complex Solvent Effects on the Optical Rotation of Chiral Molecules: A Combined Molecular Dynamics and Density Functional Theory Study
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DOI：
10.1021/acs.jpca.1c00803
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发表时间：
2021-04-08
影响因子：
2.9
通讯作者：
Crawford, T. Daniel
中科院分区：
文献类型：
--
作者：
D'Cunha, Ruhee;Crawford, T. Daniel
为手性化合物分配绝对立体化学构型的挑战可以通过精确的从头算预测旋光性来克服，旋光性是一种敏感的分子性质，由于溶剂效应而进一步复杂化。溶剂的“手性印记”——手性从溶质转移到周围的非手性溶剂——在这里用构象平均和随时间变化的密度泛函理论进行了探讨。这些复杂的溶剂效应是通过分子动力学轨迹的简单平均，以及溶质细胞活性区域内溶剂分子的显式量子力学考虑和体溶剂的隐式建模来考虑的。我们考虑了系统旋光度变化的几个轴，包括动力学轨迹的采样，单电子基集的质量，以及使用连续介质溶剂模型来解释体效应。
The challenge of assigning the absolute stereo-chemical configuration to a chiral compound can be overcome via accurate ab initio predictions of optical rotation, a sensitive molecular property that is further complicated by solvent effects. The solvent's "chiral imprint"-the transfer of the chirality from the solute to the surrounding achiral solvent-is explored here using conformational averaging and time-dependent density-functional theory. These complex solvent effects are taken into account via simple averaging over a molecular dynamics trajectory together with the explicit quantum mechanical consideration of the solvent molecules within the solute's cybotactic region and implicit modeling of the bulk solvent. We consider several axes along which the system's optical rotation varies, including the sampling of the dynamical trajectory, the quality of the one-electron basis set, and the use of continuum solvent models to account for bulk effects.