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A DFT Study of Structural and Electronic Properties of ZnS Polymorphs and its Pressure‐Induced Phase Transitions
Author(s) -
La Porta Felipe A.,
Gracia Lourdes,
Andrés Juan,
Sambrano Júlio R.,
Varela Jose A.,
Longo Elson
Publication year - 2014
Publication title -
journal of the american ceramic society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.9
H-Index - 196
eISSN - 1551-2916
pISSN - 0002-7820
DOI - 10.1111/jace.13191
Subject(s) - wurtzite crystal structure , band gap , valence (chemistry) , chemistry , formula unit , phase (matter) , condensed matter physics , materials science , crystallography , crystal structure , hexagonal crystal system , physics , organic chemistry
A systematic first‐principles investigation, by using the density functional formalism with the nonlocal B3 LYP approximation including a long‐range dispersion correction, has been performed to calculate the structural and electronic properties and phase transitions under pressure of the three phases of ZnS (cubic zinc blende, ZB , hexagonal wurtzite, W, and cubic rock salt, RS ). Numerical and analytical fittings have been carried out to determine the equilibrium unit cell geometry and equation of state parameters for the ZnS phases. The band structures, energy gap, density of states, and vibrational frequencies and their pressure dependences are investigated. The present results illustrate that both phases, W and ZB , present very similar enthalpy and the RS phase becomes thermodynamically more stable than ZB and W structures at 15.0 and 15.5 GPa, respectively. These phase transitions are accompanied by an increase of the first shell coordination number of Zn atom and by a cell volume collapse of 13.9% and 14.3% for ZB and W phases, respectively. The atomic contributions of the conduction and valence bands, as well the binding energy for the Zn 3 d orbital have been obtained.