Exploring the bonding in alkaline earth halides AeX− (Ae = Be–Ba, X = F–I) from Fermi hole localization and QTAIM perspectives†

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2024-12-28 DOI:10.1039/D4CP04332D

Luis Rincon, Valeria Bedoya, Luis E. Seijas, Vladimir Rodríguez, Cesar Zambrano and F. Javier Torres

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Abstract

A theoretical description of various [AeX]⁻ (Ae = Be–Ba, X = F–I) systems, some of which have been reported in the literature to bear an unusual quadruple bond between the metal and the halogen, is provided based on both (i) the localization of the Fermi hole and (ii) the topological analysis of the one-electron density. Insights into the bond order of various [AeX]⁻ systems are inferred on the basis of the number of electrons localized in the bond basin, the topology of the Fermi hole information computed along the bond axis, and the delocalization index. The results suggest that the [AeX]⁻ molecules present a bond with attributes closer to a classical dative bond than to a multiple one, being characterized by large stabilization due to the electrostatic interaction between the polarized metal and the halogen anion. The provided interpretation is supported by means of a comparison with the [Re₂Cl₈]²⁻ complex considered as a prototype of quadruple bonds.

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碱土卤化物AeX- （Ae=Be-Ba， X=F-I）成键的费米空穴定位和QTAIM研究

基于(i)费米空穴的局域化和（ii）单电子密度的拓扑分析，对各种[AeX]- （Ae=Be-Ba， X=F-I）体系进行了理论描述，其中一些在文献中被报道在金属和卤素之间具有不寻常的四重键。各种[AeX]-体系的键序是根据键池中的定域电子数、沿键轴计算的费米空穴拓扑信息和离域指数推断出来的。结果表明，[AeX]-分子的键属性更接近于经典的和合键，而不是多重键，其特点是由于极化金属与卤素阴离子之间的静电相互作用而具有很大的稳定性。通过与被认为是四重键原型的[Re2Cl8]2-配合物的比较，支持了上述解释。

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

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.