Second-Order Jahn–Teller (SOJT) Structural Distortions in Multiply Bonded Higher Main Group Compounds

2018 ◽  
Vol 37 (18) ◽  
pp. 2929-2936 ◽  
Author(s):  
Henry B. Wedler ◽  
Paul Wendelboe ◽  
Philip P. Power
2020 ◽  
Author(s):  
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 <i>a priori</i> modeling, and to help <i>a posteriori</i> 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 N<sup>3-</sup>, and further outline a baseline statistical knowledge of bond lengths for these compounds. We examine structural and electronic effects responsible for the functional properties and anomalous bonding behavior of inorganic nitrides, and identify promising venues for exploring uncharted compositional spaces beyond the reach of high-throughput computational methods. We find 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 inorganic nitrides with multiply-bonded metal ions as a promising venue in heterogeneous catalysis, e.g. in the development of a post-Haber-Bosch process proceeding at milder reaction conditions, thus representing further opportunity in the thriving exploration of the functional properties of this emerging class of materials.<br>


2019 ◽  
Author(s):  
Michele Pizzocchero ◽  
Matteo Bonfanti ◽  
Rocco Martinazzo

The manuscript addresses the issue of the structural distortions occurring at multiple bonds between high main group elements, focusing on group 14. These distortions are known as trans-bending in silenes, disilenes and higher group analogues, and buckling in 2D materials likes silicene and germanene. A simple but correlated \sigma + \pi model is developed and validated with first-principles calculations, and used to explain the different behaviour of second- and higher- row elements.


2001 ◽  
Author(s):  
G. D. Brabson ◽  
Maya M. Garcia ◽  
Everett W. Heinonen ◽  
Gabriel Juarez ◽  
J. D. Mather

1993 ◽  
Vol 5 (10) ◽  
pp. 1505-1516 ◽  
Author(s):  
R I Badran ◽  
S Jamila ◽  
P J Kirk ◽  
C A Bates ◽  
J L Dunn

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