We investigate the behavior of lone-pair electrons in a mixed Sb(5s)/Bi(6s) crystal-environment. Density functional theory is used to calculate the electronic properties of Sb-alloyed-Bi2WO6 and to study the effects of introducing Sb 5s orbitals to the band structure. The band edge positions, partial charge analyses, and band decomposed charge densities of BiSbWO6 are used to explain the observed trends in relative stabilities and band edge shifts. To isolate the role of the mixed lone-pair, we considered WO3 as a control model. We find that local distortions caused by Sb 5s lone-pair electrons lead to upshifts in both valence and conduction band edges.
Bibliographical noteFunding Information:
This work was supported by the National Science Foundation (NSF) grant #1609811 . All calculations were performed on Texas Advanced Computing Center (TACC) servers. Additional support was received from a National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (No. 2018R1C1B6008728).
© 2021 Elsevier B.V.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry