ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
Revised nitrides - ChemRxiv.pdf (1.48 MB)

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

preprint
revised on 30.10.2020, 16:05 and posted on 02.11.2020, 06:00 by Olivier Charles Gagné
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.

Funding

Banting post-doctoral fellowship, NSERC

Carnegie post-doctoral fellowship, Carnegie Institution for Science

History

Email Address of Submitting Author

ogagne@carnegiescience.edu

Institution

Carnegie Institution for Science

Country

United States

ORCID For Submitting Author

0000-0002-7902-8166

Declaration of Conflict of Interest

No conflict of interest

Exports