Electron Correlation Models for Optical Activity
Electron Correlation Models for Optical Activity
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光学活性的电子相关模型
DOI：
10.1063/1.1668773
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发表时间：
1968
影响因子：
4.4
通讯作者：
O. E. Weigang
中科院分区：
文献类型：
--
作者：
E. Höhn;O. E. Weigang
建立了电偶极子禁止跃迁和允许跃迁的两系统无重叠转动强度模型。得到了在生色团和环境中充分利用对称性的一般方程。详细推导了生色团与非极性各向异性微扰相互作用的(1A2←1A1(C2υ)跃迁)的电子关联项。结果表明，即使在这种零级禁忌跃迁中，极化率的微扰各向异性也有很大的贡献。同一发色团的强电偶极子允许跃迁(1A1←1A1)的关联项给出了截然不同的扇区规则。对酮的n − π*跃迁转动强度的加性计算方案表明，各向异性效应实质上改变了简单的八分规则行为，实际上有时变得更大，而这种行为发生在各向同性微扰中。由于与实验旋光强度在大小和大小上的一致是正确的。
A two‐system no‐overlap model for rotatory strength is developed for electric‐dipole forbidden as well as allowed transitions. General equations which allow for full utilization of symmetry in the chromophore and in the environment are obtained. The electron correlation terms are developed in full detail for an (1A2←1A1(C2υ) transition of a chromophore interacting with a nonpolar anisotropic perturber. It ensues that perturber anisotropy of polarizability makes substantial contributions even in such zero‐order forbidden transitions. The correlation terms for a strong electric‐dipole allowed transition (1A1←1A1) of the same chromophore gives sector rules that are decidedly different. An additive calculational scheme for the n − π* transition rotatory strengths of ketones shows the anisotropy effect to substantially modify, indeed sometimes become larger than, the simple octant rule behavior which occurs for isotropic perturbers. Since agreement with experimental rotatory strengths is correct in magnitude a...