Improved electronic structure prediction of chalcopyrite semiconductors from a semilocal density functional based on Pauli kinetic energy enhancement factor

Abstract

The correct treatment of d electrons is of prime importance in order to predict the electronic properties of the prototype chalcopyrite semiconductors. The effect of d states is linked with the anion displacement parameter u, which in turn influences the bandgap of these systems. Semilocal exchange–correlation functionals which yield good structural properties of semiconductors and insulators often fail to predict reasonable u because of the underestimation of the bandgaps arising from the strong interplay between d electrons. In the present study, we show that the meta-generalized gradient approximation (meta-GGA) obtained from the cuspless hydrogen density (MGGAC) (2019 Phys. Rev. B 100 155140) performs in an improved manner in apprehending the key features of the electronic properties of chalcopyrites, and its bandgaps are comparative to that obtained using state-of-art hybrid methods. Moreover, the present assessment also shows the importance of the Pauli kinetic energy enhancement factor, α = (τ − τ W )/τ unif in describing the d electrons in chalcopyrites. The present study strongly suggests that the MGGAC functional within semilocal approximations can be a better and preferred choice to study the chalcopyrites and other solid-state systems due to its superior performance and significantly low computational cost.

Correct and Accurate Polymorphic Energy Ordering of Transition-Metal Monoxides Obtained from Semilocal and Onsite-Hybrid Exchange-Correlation Approximations

“…In particular, we mention that SCAN+rVV10+ U , which consists of the strongly constrained and appropriately normed (SCAN) meta-GGA combined with the rVV10 van der Waals (vdW) functional and a Hubbard U correction, has been found to perform well in case of TMOs . It is clearly admitted that the meta-GGA functionals generally perform better than the GGAs in describing solid-state properties. ,− Concerning MnO, it has been shown that the polymorphic structural energy difference computed using SCAN+rVV10+ U , where U is determined from linear response theory, agrees very well with that obtained from DMC values . Besides the SCAN-based methods, several other meta-GGA functionals are also proposed and tested for solid-state properties with consistently improved accuracy. ,− Within those recent meta-GGAs, there are the functionals constructed from the cuspless hydrogen model [(revised) meta-GGA functional from cuspless hydrogen hole ((r)­MGGAC)] , that show potential promising accuracy for different challenging problems in solid-state physics. ,, It is also quite an efficient semilocal functional that can predict band gaps of bulk and layered solids with reasonable accuracy. ,− …”

Correct and accurate polymorphic energy ordering of transition-metal monoxides obtained from semilocal and onsite-hybrid exchange-correlation approximations

“…In particular, we mention that SCAN+rVV10+U , which consists of the strongly constrained and appropriately normed (SCAN) meta-GGA 43 combined with the rVV10 van der Waals (vdW) 44 functional and a Hubbard U correction, has been found to perform well in case of TMOs 11 . It is clearly admitted that the meta-GGA functionals generally perform better than the GGAs in describing solid-state properties 43, [45][46][47][48][49][50] . Concerning MnO, it has been shown that the polymorphic structural energy difference computed using SCAN+rVV10+U , where U is determined from linear response theory, agrees very well with that obtained from DMC values 11 .…”

“…Concerning MnO, it has been shown that the polymorphic structural energy difference computed using SCAN+rVV10+U , where U is determined from linear response theory, agrees very well with that obtained from DMC values 11 . Besides the SCAN-based methods, several other meta-GGA functionals are also proposed and tested for solid-state properties with consistently improved accuracy 45,[50][51][52][53][54][55][56][57][58][59][60][61] . Within those recent meta-GGAs, there are the functionals constructed from the cuspless hydrogen model [(r)MGGAC] 58,61 that show potential promising accuracy for different challenging problems in solid-state physics 50,60,61 .…”

“…Besides the SCAN-based methods, several other meta-GGA functionals are also proposed and tested for solid-state properties with consistently improved accuracy 45,[50][51][52][53][54][55][56][57][58][59][60][61] . Within those recent meta-GGAs, there are the functionals constructed from the cuspless hydrogen model [(r)MGGAC] 58,61 that show potential promising accuracy for different challenging problems in solid-state physics 50,60,61 . It is also quite an efficient semilocal functional that can predict band gaps of bulk and layered solids with reasonable accuracy 50,[61][62][63][64] .…”

“…Within those recent meta-GGAs, there are the functionals constructed from the cuspless hydrogen model [(r)MGGAC] 58,61 that show potential promising accuracy for different challenging problems in solid-state physics 50,60,61 . It is also quite an efficient semilocal functional that can predict band gaps of bulk and layered solids with reasonable accuracy 50,[61][62][63][64] .…”