General Spin Restricted Open-Shell Configuration Interaction Singles (GS-ROCIS): Implementation of Spin-Orbit Coupling and Zeeman Operators for Calculation of Optical and X-ray Absorption and Magnetic Circular Dichroism Spectra of Magnetically Coupled Transition Metal Systems.

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL
Tiago Leyser da Costa Gouveia, Lucas Lang, Dimitrios Maganas, Frank Neese
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引用次数: 0

Abstract

In this paper we present the theory and implementation of the spin-orbit coupling and Zeeman operators in the context of quasi-degenerate perturbation theory into the general spin restricted open-shell configuration interaction singles method. The implementation of the mentioned operators allows for the calculation of magnetic circularly polarized dichroism (MCD), L-edge X-ray absorption spectra (XAS) and X-ray magnetic circularly polarized dichroism (XMCD) spectra. The method was tested on calculating the MCD spectra of isostructural complexes [LCrIII(PyA)3NiII]2+, [LCrIII(PyA)3ZnII]2+and [LGaIII(PyA)3NiII]2+, with L = 1,4,7-trimethyl-1,4,7-triazacyclonanane and PyA- is the monoanion of pyridine-2-aldozime, where it correctly predicts the MCD signs of the lower optical transition of [LCrIII(PyA)3NiII]2+and [LGaIII(PyA)3NiII]2+. The capabilities of the method in computing L-edge XAS and XMCD spectra were tested on the model complexes [Cu(H2O)6]2+ and [Cu2(OAc)4(H2O)2], where it correctly calculates the L2,3-edge absorption and XMCD spectra, as well as on the antiferromagnetically coupled Cu-Fe dimer [(F8TPP)Fe(μ-O)Cu(TMPA)]+, where it correctly predicts the signs of the L2 and L3 edges of the Cu XMCD spectrum. To further illustrate the applicability of the method, the more complex L2,3-edge XAS and XMCD spectra of thiolate Fe complexes were also calculated.

一般自旋受限开壳组态相互作用单峰(GS-ROCIS):用于计算磁耦合过渡金属系统的光和x射线吸收和磁圆二色谱的自旋轨道耦合和塞曼算符的实现。
本文在准简并微扰理论的背景下,将自旋轨道耦合和塞曼算符的理论和实现转化为一般自旋受限开壳组态相互作用的单线方法。上述算子的实现允许计算磁圆偏振二色性(MCD)、l边x射线吸收光谱(XAS)和x射线磁圆偏振二色性(XMCD)光谱。在L = 1,4,7-三甲基-1,4,7-三氮杂环烷,PyA-为吡啶-2-醛脲的单阴离子条件下,计算了[LCrIII(PyA)3NiII]2+、[LCrIII(PyA)3NiII]2+、[LCrIII(PyA)3NiII]2+等同构配合物的MCD谱,正确预测了[LCrIII(PyA)3NiII]2+和[LGaIII(PyA)3NiII]2+的下光学跃迁的MCD标志。在模型配合物[Cu(H2O)6]2+和[Cu2(OAc)4(H2O)2]上测试了该方法计算l边XAS和XMCD光谱的能力,正确计算了L2、3边吸收和XMCD光谱,以及反铁磁耦合Cu-Fe二聚体[(F8TPP)Fe(μ-O)Cu(TMPA)]+,正确预测了Cu XMCD光谱的L2和L3边的符号。为了进一步说明该方法的适用性,还计算了硫代铁配合物更复杂的L2、3边XAS和XMCD光谱。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
The Journal of Physical Chemistry A
The Journal of Physical Chemistry A 化学-物理:原子、分子和化学物理
CiteScore
5.20
自引率
10.30%
发文量
922
审稿时长
1.3 months
期刊介绍: The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
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