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Issue 17, 2020
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Peculiar bond characters of fivefold coordinated octet compound crystals

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Abstract

The present work exemplifies complementary perspectives offered by the band and bond pictures of solids, with an emphasis on the chemical intuition pertaining to the latter, especially in the presence of interfaces. The modern computational method of constructing a unique set of maximally localized Wannier functions from delocalized band states imparts new interpretations to the familiar concept of chemical bonds in the context of crystalline solids. By bridging the band and bond pictures using advanced computational tools, we reveal for the first time the unusual bond characters of a long-predicted fivefold coordinated structure of binary octet compounds ANB8−N consisting of AA′ stacked planar AB honeycombs. While the isolated monolayer retains the familiar pz–π bonding in a honeycomb framework as in graphene and hexagonal boron nitride, the bulk foregoes in-plane π bonding and embraces out-of-plane ⋯A–B–A–B⋯ chain bonding via overlapping pz orbitals. Not only does the chemical intuition gained by invoking the bond picture clarify the chemical nature of the fivefold coordination, but it also facilely explains a salient discrepancy in theoretical predictions in otherwise sound ample experimental evidence in the form of epitaxial thin films, paving the way towards rational synthesis of such thin films for optoelectronic applications. On the other hand, we show that the conduction band minimum, important in determining the electrical and optical properties, is a distinctly extended state that can only be properly described within the band picture.

Graphical abstract: Peculiar bond characters of fivefold coordinated octet compound crystals

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Supplementary files

Article information


Submitted
16 Jan 2020
Accepted
26 Mar 2020
First published
27 Mar 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020,11, 4340-4350
Article type
Edge Article

Peculiar bond characters of fivefold coordinated octet compound crystals

A. Sun, S. Gao and G. Gu, Chem. Sci., 2020, 11, 4340
DOI: 10.1039/D0SC00292E

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