This work presents the first simulations of the full optical rotation (OR) tensor at coupled cluster with single and double excitations (CCSD) level in the modified velocity gauge (MVG) formalism. The CCSD‐MVG OR tensor is origin independent, and each tensor element can in principle be related directly to experimental measurements on oriented systems. We compare the CCSD results with those from two density functionals, B3LYP and CAM‐B3LYP, on a test set of 22 chiral molecules. The results show that the functionals consistently overestimate the CCSD results for the individual tensor components and for the trace (which is related to the isotropic OR), by 10%–20% with CAM‐B3LYP and 20%–30% with B3LYP. The data show that the contribution of the electric dipole–magnetic dipole polarizability tensor to the OR tensor is on average twice as large as that of the electric dipole–electric quadrupole polarizability tensor. The difficult case of (1S,4S)‐(–)‐norbornenone also reveals that the evaluation of the former polarizability tensor is more sensitive than the latter. We attribute the better agreement of CAM‐B3LYP with CCSD to the ability of this functional to better reproduce electron delocalization compared with B3LYP, consistent with previous reports on isotropic OR. The CCSD‐MVG approach allows the computation of reference data of the full OR tensor, which may be used to test more computationally efficient approximate methods that can be employed to study realistic models of optically active materials.

中文翻译：

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改进速度计中具有单激发和双激发水平的耦合簇上的全旋光张量

这项工作提出了在改进的速度计（MVG）形式上的具有单激发和双激发（CCSD）的耦合簇上的全旋光（OR）张量的第一个模拟。CCSD-MVG OR张量是与原点无关的，每个张量元素原则上都可以直接与定向系统上的实验测量相关。在22个手性分子的测试集上，我们将CCSD结果与两个密度泛函B3LYP和CAM-B3LYP的结果进行了比较。结果表明，功能始终高估单个张量分量和迹线（与各向同性OR）有关的CCSD结果，使用CAM-B3LYP时高10％–20％，使用B3LYP时高20％–30％。数据表明，电偶极子-磁偶极子极化率张量对“或”张量的贡献平均是电偶极子-电四极子极化率张量的两倍。（1的困难情况S，4 S）-（-）-降冰片烯酮还表明，前者极化率张量的评估比后者更敏感。我们将CAM‐B3LYP与CCSD的更好协议归因于该功能与B3LYP相比能够更好地重现电子离域的能力，这与先前有关各向同性OR的报道一致。CCSD-MVG方法允许计算完整OR张量的参考数据，可用于测试计算效率更高的近似方法，这些方法可用于研究光学活性材料的逼真的模型。