Y2M3Si5 (M = Mn-Cu, Tc-Pd, Re-Pt)的化学键化趋势:广义R2M3X5金属间族的研究

IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR
Giorgio Palla,Linda S Reitz,Riccardo Freccero,Serena De Negri,Richard Dronskowski
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引用次数: 0

摘要

对Y2M3Si5 (M = Mn-Cu, Tc-Pd, Re-Pt)金属间化合物中的化学键进行了比较分析,旨在阐明控制其结晶成四方(tP40-Sc2Fe3Si5)、单斜(mS40-Lu2Co3Si5)或正交(oI40-U2Co3Si5)结构的化学因素。本研究首次全面研究了Y2M3Si5化合物与M = Fe, Co和Ni的键合,每种化合物都采用三种结构类型中的一种。通过预测晶体轨道汉密尔顿人口曲线(pCOHP)、集成pCOHP (IpCOHP)和集成晶体轨道键指数(ICOBI)分析,发现成键主要由极性共价M-Si相互作用主导,其次是Y-Si, Si-Si键起次要作用。这突出了一个比Zintl概念所预测的更复杂的键合图。将分析扩展到所有过渡金属和原型,无论其热力学稳定性如何,都可以系统地比较稳定和亚稳构型的键合。单位胞内的共价分布,量化为IpCOHP%,在过渡金属系列中呈现周期性趋势,包括顺周期和下行基团。M-Si IpCOHP%的最大化是稳定一种结构类型的关键化学因素,与实验观察结果一致。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Chemical Bonding Trends in Y2M3Si5 (M = Mn-Cu, Tc-Pd, Re-Pt): A Study within the Broad R2M3X5 Intermetallic Family.
A comparative analysis of the chemical bonding in the Y2M3Si5 (M = Mn-Cu, Tc-Pd, Re-Pt) intermetallic compounds is presented, aiming at elucidating the chemical factors governing their crystallization into tetragonal (tP40-Sc2Fe3Si5), monoclinic (mS40-Lu2Co3Si5), or orthorhombic (oI40-U2Co3Si5) structures. This study provides the first comprehensive bonding investigation of Y2M3Si5 compounds with M = Fe, Co, and Ni, each adopting one of the three structure types. Employing projected crystal orbital Hamilton population curves (pCOHP), integrated pCOHP (IpCOHP), and integrated crystal orbital bond index (ICOBI) analyses, the bonding scenario is revealed to be primarily dominated by polar covalent M-Si interactions, followed by Y-Si, with Si-Si bonds playing a secondary role. This highlights a bonding picture more complex than that predicted by the Zintl concept. Extending the analysis to all transition metals and prototypes, regardless of their thermodynamic stability, allows for a systematic comparison of bonding in both stable and metastable configurations. The covalency distribution within the unit cell, quantified as IpCOHP%, exhibits periodic trends across the transition metal series, both along periods and down groups. The maximization of M-Si IpCOHP% emerges as the key chemical factor in stabilizing one structure type over another, aligning with experimental observations.
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来源期刊
Inorganic Chemistry
Inorganic Chemistry 化学-无机化学与核化学
CiteScore
7.60
自引率
13.00%
发文量
1960
审稿时长
1.9 months
期刊介绍: Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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