: 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.

Stability, Chemical Bonding, and Electron Lone Pair Localization in AsN at High Pressure by Density Functional Theory Calculations / Sukserm, Akkarach; Ceppatelli, Matteo; Serrano-Ruiz, Manuel; Scelta, Demetrio; Dziubek, Kamil; Morana, Marta; Bini, Roberto; Peruzzini, Maurizio; Bovornratanaraks, Thiti; Pinsook, Udomsilp; Scandolo, Sandro. - In: INORGANIC CHEMISTRY. - ISSN 0020-1669. - STAMPA. - 63:(2024), pp. 8142-8154. [10.1021/acs.inorgchem.4c00342]

Stability, Chemical Bonding, and Electron Lone Pair Localization in AsN at High Pressure by Density Functional Theory Calculations

Ceppatelli, Matteo
;
Morana, Marta;Bini, Roberto;Peruzzini, Maurizio;
2024

Abstract

: 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.
2024
63
8142
8154
Sukserm, Akkarach; Ceppatelli, Matteo; Serrano-Ruiz, Manuel; Scelta, Demetrio; Dziubek, Kamil; Morana, Marta; Bini, Roberto; Peruzzini, Maurizio; Bovornratanaraks, Thiti; Pinsook, Udomsilp; Scandolo, Sandro
File in questo prodotto:
File Dimensione Formato  
(177)Inor.Chem.AsN.pdf

Accesso chiuso

Tipologia: Pdf editoriale (Version of record)
Licenza: Solo lettura
Dimensione 7.3 MB
Formato Adobe PDF
7.3 MB Adobe PDF   Richiedi una copia

I documenti in FLORE sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/1360452
Citazioni
  • ???jsp.display-item.citation.pmc??? 0
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact