On the electronic structure and stability of icosahedralr-X2Z10H12 and Z12H122−clusters; r = {ortho, meta, para}, X = {C, Si}, Z = {B, Al}‡

文献信息

发布日期 2010-03-26
DOI 10.1039/B924322D
影响因子 3.676
作者

Paul von Ragué Schleyer, Gabriel Aullón, José I. Burgos, Antonio Fernández-Barbero, Ibon Alkorta


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摘要

We report on the electronic structure of the 12-vertex icosahedral clusters r-X2Z10H12 and Z12H122–, where X = {C, Si} and Z = {B, Al}. The least stable cluster—with the lowest HOMO–LUMO gap (Eg)—corresponds to the ortho-X2Z10H12 isomers for all values of X = {C, Si} and Z = {B, Al}. The well-known energetic order E(para) < E(meta) < E(ortho) for r-carboranes is also valid for all compounds except r-C2Al10H12. Substitution of two atoms of carbon or silicon into the icosahedral cage B12H122− enhances considerably the stability of the system as analyzed from Eg gaps, as opposite to Al12H122−, where similar gaps are found upon double carbon or silicon substitution regardless of the positions in the cage. In order to highlight similarities and differences in the title clusters, topological analysis of the electron density was performed, together with analysis of the deviation from polyhedron icosahedral form with (i) volumes, skewness and kurtosis calculations; and (ii) continuous shape measures.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

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.

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