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首页> 外文期刊>Zeitschrift fur Naturforschung. A, A journal of physical sciences >~(121)Sb NMR and SCF-MS-Xα Studies of Quadrupole Interaction and The Electronic Structure of Mixed-Valence Compound, Cs_2SbCl_6
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~(121)Sb NMR and SCF-MS-Xα Studies of Quadrupole Interaction and The Electronic Structure of Mixed-Valence Compound, Cs_2SbCl_6

机译：〜（121）Sb NMR和SCF-MS-Xα研究四极相互作用和混合价化合物Cs_2SbCl_6的电子结构

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摘要

Cs_2SbCl_6 is known as a typical mixed-valence compound. It crystallizes into a tetragonal space group 14_1/amd and contains two different complex anions, Sb(Ⅲ)Cl_6~(3-) and Sb(Ⅴ)Cl_6~-. The dark blue color of this compound has been considered to originate from a charge transfer between the above two anions. In order to study the electronic structure of these complex anions and the existence of charge transfer between them we measured the ~(121)Sb NMR spectrum and carried out molecular orbital calculations on the electronic states of these anions. The ~(121)Sb NMR spectrum consists of two peaks at 0 and 30 kHz which can be assigned to the central transition of ~(121)Sb in Sb(Ⅴ)Cl_6~- and Sb(Ⅲ)Cl_6~(3-), respectively. The line shape analyses of the spectra led to nuclear quadrupole coupling constants of nearly zero for Sb(Ⅴ)Cl_6~- and 4.9 ± 0.5 MHz for Sb(Ⅲ)Cl_6~(3-) at room temperature. The quadrupole coupling constant of Sb(Ⅲ) decreases steadily on heating. The calculations of the electronic ground state energies of both anions were calculated by the MS-Xα molecular orbital method. The calculated charge-transfer band from the A_(1g) state of Sb(Ⅲ)Cl_6~(3-) to the A_(1g) state of Sb(Ⅴ)Cl_6~- appears at 610 nm and can account for the experimental electronic spectrum, the calculated quadrupole coupling constant in Sb(Ⅲ)Cl_6~(3-) however is far larger than the experimental one. The contribution of the charge-transferred state to the ground state is negligible and so the temperature dependence of the quadrupole coupling constant of ~(121)Sb(Ⅲ) is attributed to an anisotropic thermal expansion of the compound.
机译：Cs_2SbCl_6被称为典型的混合价化合物。它结晶成一个方形空间群14_1 / amd，并包含两个不同的配位阴离子Sb（Ⅲ）Cl_6〜（3-）和Sb（Ⅴ）Cl_6〜-。该化合物的深蓝色被认为源自上述两个阴离子之间的电荷转移。为了研究这些复杂阴离子的电子结构以及它们之间电荷转移的存在，我们测量了〜（121）Sb NMR光谱，并对这些阴离子的电子态进行了分子轨道计算。 〜（121）Sb NMR光谱由0和30 kHz处的两个峰组成，可以分配给Sb（Ⅴ）Cl_6〜-和Sb（Ⅲ）Cl_6〜（3-）中〜（121）Sb的中心跃迁。 ， 分别。光谱的线形分析在室温下导致Sb（Ⅴ）Cl_6〜-的核四极偶合常数接近零，而Sb（Ⅲ）Cl_6〜（3-）的核四极偶合常数为4.9±0.5 MHz。 Sb（Ⅲ）的四极耦合常数在加热时稳定降低。通过MS-Xα分子轨道方法计算了两个阴离子的电子基态能。计算得出的从Sb（Ⅲ）Cl_6〜（3-）的A_（1g）态到Sb（Ⅴ）Cl_6〜-的A_（1g）态的电荷转移带出现在610 nm处，可以解释实验电子在Sb（Ⅲ）Cl_6〜（3-）光谱中，计算出的四极耦合常数远大于实验值。电荷转移态对基态的贡献可忽略不计，因此〜（121）Sb（Ⅲ）的四极偶合常数的温度依赖性归因于化合物的各向异性热膨胀。

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