Integrated Continuum Dielectric Approaches to treat Molecular Polarizability and the Condensed Phase: Refractive Index and Implicit Solvation.
Integrated Continuum Dielectric Approaches to treat Molecular Polarizability and the Condensed Phase: Refractive Index and Implicit Solvation.
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处理分子极化性和凝聚相的集成连续介电方法：折射率和隐式溶剂化。
DOI：
10.1021/ct900029d
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发表时间：
2009
影响因子：
5.5
通讯作者：
Bayly,ChristopherI
中科院分区：
文献类型：
--
作者：
Truchon,Jean-François;Nicholls,Anthony;Roux,Benoît;Iftimie,RaduI;Bayly,ChristopherI
使用分子内的介电连续体来准确地模拟分子的极化率的想法被扩展到包括更大的生物有机分子和凝聚相的光谱。原子极化半径和内部介电常数(εIn)被用来再现从头算B3LYP/AUG-CC-pVTZ极化张量。各向同性极化率和各向异性的平均无符号误差分别为2.6%和5.2%。结果表明，通常的泊松−波尔兹曼接触半径和较低的内部介电系数是不合适的，需要进行重大修改。为了考虑极化率的各向异性，内部介电(εIn)常数需要大于6.0.重新解释了εIn与实验折射率(N)之间的理论联系，这项研究表明，对于覆盖整个n范围的23个有机分子，即使在εIn=24的情况下，所得到的折射率也可以与实验很好地关联(斜率为1.00，截距为0.05，R=0.95)。用来计算宏观类折射率的新方法表明，EPIC参数化法应用于凝聚相导致了合适的行为。虽然发展EPIC的主要目标是在显式溶剂计算中包括极化率，但我们也将该模型扩展到使用隐式溶剂。这需要使用三区平滑介电函数来从分子内的极化介电过渡到溶剂的介电连续谱。根据485个实验水化自由能对该模型进行了参数化和验证。在8个溶剂腔原子半径和单一表面张力条件下，平均无符号误差为1.1kal/mol，相关系数为0.9，验证了EPIC模型在凝聚相的应用。
The idea of using a dielectric continuum inside a molecule to accurately model molecular polarizability is extended to include a larger spectrum of bioorganic molecules and the condensed phase. Atomic polarization radii and an internal dielectric (εin) were fitted to reproduce ab initio B3LYP/aug-cc-pVTZ polarizability tensors taken from a data set of 707 molecules. The average unsigned error on the isotropic polarizability and anisotropy are 2.6% and 5.2%, respectively. It is shown that usual Poisson−Boltzmann contact radii and a low internal dielectric are not appropriate and require major revision. To account for the anisotropy of polarizability, the internal dielectric (εin) constant needs to be larger than 6.0. Reinterpreting the theoretical link between εinand the experimental refractive index (n), this study shows, with a set of 23 organic molecules spanning the entire range ofn, that even with εin= 24 the obtained refractive indices can correlate well with experiment (slope of 1.00, intercept of 0.05, and R = 0.95). The novel methodology used here to calculate a macroscopic-like refractive index shows that the application of the EPIC parametrization to condensed phase leads to suitable behavior. Although the primary goal in developing EPIC was to include polarizability in explicit solvent calculations, we also extend the model to work with implicit solvent. This requires the use of a 3-zone smooth dielectric function to transition from the polarization dielectric inside the molecules to the dielectric continuum of the solvent. The parametrization and validation of this model are performed against 485 experimental free energies of hydration. Using 8 solvent cavity atomic radii and a single surface tension an average unsigned error of 1.1 kal/mol and a correlation coefficient of 0.9 are obtained, validating the use of the EPIC model in the condensed phase.
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DOI：
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发表时间：
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期刊：
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