On the Crystal Chemistry of Inorganic Nitrides: Crystal-Chemical Parameters, Bonding Behavior, and Opportunities in the Exploration of Their Compositional Space

02 November 2020, Version 4
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The scarcity of nitrogen in Earth’s crust, combined with challenging synthesis, have made inorganic nitrides a relatively unexplored class of compounds compared to their naturally-abundant oxide counterparts. To facilitate exploration of their compositional space via a priori modeling, and to help a posteriori structure verification not limited to inferring the oxidation state of redox-active cations, we derive a suite of bond-valence parameters and Lewis-acid strength values for 76 cations observed bonding to N3-, and further outline a baseline statistical knowledge of bond lengths for these compounds. Examination of structural and electronic effects responsible for the functional properties and anomalous bonding behavior of inorganic nitrides shows that many mechanisms of bond-length variation ubiquitous to oxide and oxysalt compounds (e.g., lone-pair stereoactivity, the Jahn-Teller and pseudo Jahn-Teller effects) are similarly pervasive in inorganic nitrides, and are occasionally observed to result in greater distortion magnitude than their oxide counterparts. We identify promising functional units for exploring uncharted chemical spaces of inorganic nitrides, e.g. multiple-bond metal centers with promise regarding the development of a post-Haber-Bosch process proceeding at milder reaction conditions, and promote an atomistic understanding of chemical bonding in nitrides relevant to such pursuits as the development of a model of ion substitution in solids, a problem of great relevance to semiconductor doping whose resolve would fast-track the development of compound solar cells, battery materials, electronics, and more.

Keywords

Inorganic chemistry
Exploratory Synthesis
bond-valence parameters
nitrides
Lewis acidity
bond lengths
Vibronic Mixing
lone-pair stereoactivity
structure-property relationships

Comments

Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.