An ab Initio Linear Response Method for Computing Magnetic Circular Dichroism Spectra with Nonperturbative Treatment of Magnetic Field
An ab Initio Linear Response Method for Computing Magnetic Circular Dichroism Spectra with Nonperturbative Treatment of Magnetic Field
复制标题
磁场非微扰处理计算磁圆二色谱的从头线性响应方法
DOI：
10.1021/acs.jctc.9b00095
复制
发表时间：
2019
影响因子：
5.5
通讯作者：
Li, Xiaosong
中科院分区：
文献类型：
--
作者：
Sun, Shichao;Williams-Young, David;Li, Xiaosong
磁性圆二色性（MCD）实验为探索化学配合物和凝聚态体系的几何、磁性和电子性质提供了一种灵敏的工具。它们的模拟也具有挑战性，因为需要同时处理有限磁场和光场的扰动。在这项工作中，我们引入了一种从头开始的方法，用伦敦轨道非摄动地处理外磁场，以模拟闭壳系统的MCD谱。在无自旋的非相对论性哈密顿量中包含了磁场的变化效应，然后用线性响应形式直接计算了左右圆偏振光的吸收差。除了基本的数学形式和实现之外，本文开发的方法已应用于阴离子钠、2,2,6,6-四甲基环己酮和3-甲基-2-己酮的MCD光谱的模拟。对结果进行了讨论，并与实验进行了比较。
Magnetic circular dichroism (MCD) experiments provide a sensitive tool for exploring geometric, magnetic, and electronic properties of chemical complexes and condensed matter systems. They are also challenging to simulate because of the need to simultaneously treat the perturbations of a finite magnetic field as well as an optical field. In this work, we introduce an ab initio approach that treats the external magnetic field nonperturbatively with London orbitals for simulating the MCD spectra of closed-shell systems. Effects of a magnetic field are included variationally in the spin-free nonrelativistic Hamiltonian, followed by a linear response formalism to directly calculate the difference in absorption between the left and right circularly polarized light. In addition to the presentation of underlying mathematical formalism and implementation, the method developed in this paper has been applied to simulations of MCD spectra of the sodium anion, 2,2,6,6-tetramethylcyclohexanone, and 3-methyl-2-hexanone. Results are discussed and compared to experiments.