三维 Zn[M(CN)4] 四氰酸酯（M = Ni、Pd 和 Pt）的电子结构和光学性质的计算和实验测定,The Journal of Physical Chemistry C

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三维 Zn[M(CN)4] 四氰酸酯（M = Ni、Pd 和 Pt）的电子结构和光学性质的计算和实验测定
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2023-08-03 , DOI: 10.1021/acs.jpcc.3c03013
Rodrigo Mojica ₁ , Ana Elizabeth Torres ₂ , Ana Adela Lemus-Santana ₁ , Raúl Borja-Urby ₃ , Yosuan Avila ₁ , Edilso Reguera ₁

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通过光谱技术和基于 DFT 的计算计算，研究了氰化物基 Zn[M(CN) _{4 ]（M = Ni、Pd 和 Pt）配位聚合物的电子结构。}当四氰酸酯部分的内部金属 [M(CN) ₄由于 π 背键合现象产生的电荷分布以及 M 和 Zn 的极化功率之间的竞争，] 从 Ni 变为 Pt，以及 Ni 变为 Pd。红外、拉曼和紫外-可见光谱技术与混合 HSE06 计算相结合证明了这一点。样品表征通过 XPS 光谱和 HR-TEM 图像完成。还通过计算的 lm 分解态密度和能带色散图研究了电子结构。价带顶部和导带底部的性质由 dM、pM、p-氮和 c-碳杂化轨道描述。前一种固体的电子行为与孤立的方形平面四氰酸酯的电子行为有很大不同，但 HOMO-LUMO 电子跃迁仍然由四氰酸酯 [M(CN)₄ ] 和 π-π* 相互作用在三种情况下。报告了所研究的三种半导体的带隙能量值，并分析了内部金属效应。讨论了与能隙相关的电子跃迁的间接性质，并报告了有效质量和折合质量的值。

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Computational and Experimental Determination of the Electronic Structure and Optical Properties of Three-Dimensional Zn[M(CN)4] Tetracyanates (M = Ni, Pd, and Pt)

The electronic structure of cyanide-based Zn[M(CN)₄] (M = Ni, Pd, and Pt) coordination polymers is studied by means of spectroscopic techniques and DFT-based computational calculations. The observed different ν(CN) band shifts to higher frequencies when the inner metal from the tetracyanate moiety [M(CN)₄] changes from Ni to Pt and Ni to Pd as a consequence of the charge distribution produced by the π back-bonding phenomena and the competition between the polarization powers from M and Zn. This is evidenced by infrared, Raman, and UV–vis spectroscopic techniques in conjunction with hybrid HSE06 calculations. The sample characterization was completed from XPS spectra and HR-TEM images. The electronic structure was also studied by the computed lm-decomposed density of states and band dispersion diagrams. The nature of the valence band top and conduction band bottom is described by d-M, p-M, p-nitrogen, and c-carbon hybridized orbitals. The electronic behavior of the former solids strongly differs from that of the isolated square-planar tetracyanates, but the HOMO–LUMO electronic transitions are still dominated by the tetracyanate [M(CN)₄] and π–π* interactions in the three cases. Band gap energy values are reported for the three studied semiconductors, and the internal metal effect is analyzed. The indirect nature of the electronic transitions associated with the gap is discussed, and the values of the effective and reduced masses are reported.

更新日期：2023-08-03

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