Stability, Chemical Bonding, and Electron Lone Pair Localization in AsN at High Pressure by Density Functional Theory Calculations
- Autor(en)
- Akkarach Sukserm, Matteo Ceppatelli, Manuel Serrano-Ruiz, Demetrio Scelta, Kamil Dziubek, Marta Morana, Roberto Bini, Maurizio Peruzzini, Thiti Bovornratanaraks, Udomsilp Pinsook, Sandro Scandolo
- Abstrakt
The covalent bonding framework of crystalline single-bonded cubic AsN, recently synthesized under high pressure and high temperature conditions in a laser-heated diamond anvil cell, is here studied by means of density functional theory calculations and compared to single crystal X-ray diffraction data. The precise localization of the nonbonding electron lone pairs and the determination of their distances and orientations are related to the presence of characteristic structural motifs and space regions of the unit cell dominated by repulsive electronic interactions, with the relative orientation of the electron lone pairs playing a key role in minimizing the energy of the structure. We find that the vibrational modes associated with the expression of the lone pairs are strongly localized, an observation that may have implications for the thermal conductivity of the compound. The results indicate the thermodynamic stability of the experimentally observed structure of AsN above ∼17 GPa, provide a detailed insight into the nature of the chemical bonding network underlying the formation of this compound, and open new perspectives to the design and high pressure synthesis of new pnictogen-based advanced materials for potential applications of energetic and technological relevance.
- Organisation(en)
- Institut für Mineralogie und Kristallographie
- Externe Organisation(en)
- Chulalongkorn University, Ministry of Higher Education, Science, Research and Innovation, Consiglio Nazionale delle Ricerche, European Laboratory for Non-Linear Spectroscopy (LENS), Università degli Studi di Firenze, Abdus Salam International Centre for Theoretical Physics
- Journal
- Inorganic Chemistry
- Band
- 63
- Seiten
- 8142-8154
- Anzahl der Seiten
- 13
- ISSN
- 0020-1669
- DOI
- https://doi.org/10.1021/acs.inorgchem.4c00342
- Publikationsdatum
- 05-2024
- Peer-reviewed
- Ja
- ÖFOS 2012
- 105113 Kristallographie, 104003 Anorganische Chemie, 104022 Theoretische Chemie, 103009 Festkörperphysik
- Schlagwörter
- ASJC Scopus Sachgebiete
- Physical and Theoretical Chemistry, Inorganic Chemistry
- Link zum Portal
- https://ucrisportal.univie.ac.at/de/publications/4e18e38d-da12-40ae-8270-b6478173199b