A molecular orbital selection approach for fast calculations of specific rotation with density functional theory
A molecular orbital selection approach for fast calculations of specific rotation with density functional theory
复制标题
利用密度泛函理论快速计算比旋光度的分子轨道选择方法
DOI：
10.1002/chir.23158
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发表时间：
2019
期刊：
影响因子：
2
通讯作者：
Caricato, Marco
中科院分区：
文献类型：
--
作者：
Aharon, Tal;Caricato, Marco
在这项工作中，我们描述了一种选择最重要的分子轨道（MO）来通过线性响应（LR）Kohn-Sham密度泛函理论（KS-DFT）计算旋光张量的简单方法。利用常用于求解 LR 方程的算法的迭代性质，我们选择对猜测扰动密度贡献大于某个阈值的 MO，并仅使用所选 MO 求解 LR 方程。我们提出了两个选择标准，以及两个选择阈值的定义。然后，我们使用两个泛函（B3LYP 和 CAM-B3LYP）和两个基组（aug-cc-pVDZ 和 aug-cc-pVTZ）在一组 51 个有机分子上测试该方法，这些有机分子的比旋光度跨越五个数量级，100–104deg (dm−1(g/mL)−1)。我们表明，这种方法确实可以提供非常准确的比旋度值，估计加速比在最保守的选择标准下为 2 至 8 倍，在中间标准下可达 20 至 30 倍。
In this work, we describe a simple approach to select the most important molecular orbitals (MOs) to compute the optical rotation tensor through linear response (LR) Kohn‐Sham density functional theory (KS‐DFT). Taking advantage of the iterative nature of the algorithms commonly used to solve the LR equations, we select the MOs with contributions to the guess perturbed density that are larger than a certain threshold and solve the LR equations with the selected MOs only. We propose two criteria for the selection, and two definitions of the selection threshold. We then test the approach with two functionals (B3LYP and CAM‐B3LYP) and two basis sets (aug‐cc‐pVDZ and aug‐cc‐pVTZ) on a set of 51 organic molecules with specific rotation spanning five orders of magnitude, 100–104deg (dm−1(g/mL)−1). We show that this approach indeed can provide very accurate values of specific rotation with estimated speedup that ranges from 2 to 8× with the most conservative selection criterion, and up to 20 to 30× with the intermediate criterion.