Structure, non-stoichiometry, and geometrical frustration of alpha-tetragonal boron

TL;DR

This study uses density functional theory to analyze the structure, non-stoichiometry, and geometrical frustration in pure alpha-tetragonal boron, revealing its near-stoichiometric nature and residual entropy due to site occupation.

Contribution

It provides a detailed theoretical characterization of pure alpha-tetragonal boron, clarifying its structural stability, site occupation preferences, and geometrical frustration, distinguishing it from other boron forms.

Findings

Pure alpha-tetragonal boron is nearly stoichiometric at B52 with residual entropy.

Residual entropy is comparable to beta-rhombohedral boron, indicating geometrical frustration.

Deviations from stoichiometry are small and temperature-dependent.

Abstract

Recent discoveries of supposedly pure alpha-tetragonal boron require to revisit its structure. The system is also interesting with respect to a new type of geometrical frustration in elemental crystals, which was found in beta-rhombohedral boron. Based on density functional theory calculations, the present study has resolved the structural and thermodynamic characteristics of pure alpha-tetragonal boron. Different from beta-rhombohedral boron, the conditions for stable covalent bonding (a band gap and completely filled valence bands) are almost fulfilled at a composition B_52 with two 4c interstitial sites occupied. This indicates that the ground state of pure alpha-tetragonal boron is stoichiometric. However, the covalent condition is not perfectly fulfilled because non-bonding in-gap states exist that cannot be eliminated. The half occupation of the 4c sites yields a macroscopic amount of residual entropy, which is as large as that of beta-rhombohedral boron. Therefore, alpha-tetragonal boron can be classified as an elemental crystal with geometrical frustration. Deviations from stoichiometry can occur only at finite temperatures. Thermodynamic considerations show that deviations delta from the stoichiometric composition B_(52+delta) are small and positive. For reported high-pressure syntheses conditions delta is predicted to be about 0.1 to 0.2. An important difference between pure and C- or N-containing alpha-tetragonal boron is found in the occupation of interstitial sites: the pure form prefers to occupy the 4c sites, whereas in C- or N-containing forms a mixture of 2a, 8h, and 8i sites are occupied. The present article provides relations of site occupation, delta values, and lattice parameters, which enable us to identify pure alpha-tetragonal and distinguish the pure form from other ones.