A study of optical properties and electron energy loss spectra of ZnS by linear response theory

Abstract The linear response theory has been applied to study the optical properties and electron energy loss spectra of ZnS. The ground state is built using the Full-Potential Linearized Augmented Plane Wave method. Thereafter, the electronic properties such as band structure and density of states are calculated. Calculations of electron energy loss spectra and optical properties are performed on the top of these ground state electronic properties. The calculations are performed using three exchange–correlation kernels namely, adiabatic local density approximation, long range contribution, and the bootstrap. The random phase approximation is also considered. An approach proposed by us to find the material dependent parameter <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mi>α</mml:mi> </mml:math> is used in long range contribution kernel to capture more accurate optical properties. Three values of <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mi>α</mml:mi> </mml:math> viz 0.78, 1.09, and 1.22 are considered. It is observed that the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:mi>α</mml:mi> </mml:math> = 0.78 gives very good results. This proposed scheme is found to work very well for ZnS also. The effect of local field and electron–hole interaction on the spectra is examined. For example after incorporating local field effect the high frequency dielectric constant <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:msub> <mml:mrow> <mml:mi>ε</mml:mi> </mml:mrow> <mml:mrow> <mml:mi>∞</mml:mi> </mml:mrow> </mml:msub> </mml:math> [i.e. <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" overflow="scroll"> <mml:msub> <mml:mrow> <mml:mi>ε</mml:mi> </mml:mrow> <mml:mrow> <mml:mn>1</mml:mn> </mml:mrow> </mml:msub> <mml:mrow> <mml:mfenced close=")" open="(" separators=""> <mml:mrow> <mml:mi>E</mml:mi> <mml:mo>→</mml:mo> <mml:mn>0</mml:mn> <mml:mi>e</mml:mi> <mml:mi>V</mml:mi> </mml:mrow> </mml:mfenced> </mml:mrow> </mml:math> ], reduces by 9.19, 12.26, 13.51 and 11.02% for random phase approximation, adiabatic local density approximation, long range contribution and bootstrap kernel respectively. In EELS plasmon peak positions are found using the three kernels and random phase approximation. A good accord with experimental results is noted after incorporating local field effects. It is observed that local field effect causes redshift of prominent peak (i.e. plasmon peak) in electron energy loss spectra by 0.61 eV.