Modulation of optical absorption in m-Fe1-xRuxS2 and exploring stability in new m-RuS2

A first-principle computational method has been used to investigate the effects of Ru dopants on the electronic and optical absorption properties of marcasite FeS2. In addition, we have also revealed a new marcasite phase in RuS2, unlike most studied pyrite structures. The new phase has fulfilled all the necessary criteria of structural stability and its practical existence. The transition pressure of 8 GPa drives the structural change from pyrite to orthorhombic phase in RuS2. From the thermodynamical calculation, we have reported the stability of new-phase under various ranges of applied pressure and temperature. Further, from the results of phonon dispersion calculated at Zero Point Energy, pyrite structure exhibits ground state stability and the marcasite phase has all modes of frequencies positive. The newly proposed phase is a semiconductor with a band gap comparable to its pyrite counterpart but vary in optical absorption by around 10(6) cm(-1). The various Ru doped structures have also shown similar optical absorption spectra in the same order of magnitude. We have used crystal field theory to explain high optical absorption which is due to the involvement of different electronic states in formation of electronic and optical band gaps. L0wdin charge analysis is used over the customarily Mulliken charges to predict 89% of covalence in the compound. Our results indicate the importance of new phase to enhance the efficiency of photovoltaic materials for practical applications.

Automated summary

A first-principle computational method was used to study the effects of Ru dopants on the electronic and optical absorption properties of marcasite FeS2, and a new marcasite phase in RuS2 was discovered. The new phase showed structural stability and semiconductor properties. The research also revealed the transition pressure from pyrite to orthorhombic phase in RuS2 and the impact of different electronic states on optical absorption.