Insights into first-principles characterization of the monoclinic VO2(B) polymorph via DFT + U calculation: electronic, magnetic and optical properties

We have studied the structural, electronic, magnetic, and optical properties of the VO₂(B) polymorph using first-principles calculations based on density functional theory (DFT). This polymorph was found to display four optimized structures namely VO₂(B)_PP, VO₂(B)_LP, VO₂(B)_PPD, and VO₂(B)_LPD using the generalized gradient approximation (GGA) PBE exchange-correlation functional by including/excluding van der Waals interaction. Our derivation provides a theoretical justification for adding an on-site Coulomb U value in the conventional DFT calculations to allow a direct comparison of the two methods. We predicted a zero bandgap of the VO₂(B) structure based on GGA/PBE. However, by GGA/PBE + U, we found accurate bandgap values of 0.76, 0.66, and 0.70 eV for VO₂(B)_PP, VO₂(B)_LP, and VO₂(B)_PPD, respectively. The results obtained from DFT + U were accompanied by a structural transition from the metallic to semiconductor property. Here, we verified the non-magnetic characteristic of the monoclinic VO₂(B) phase with some available experimental and theoretical data. However, the debate on the magnetic property of this polymorph remains unresolved. Imaginary and real parts of the dielectric function, as computed with the GGA/PBE functional and the GGA/PBE + U functional, were also reported. The first absorption peaks of all considered geometries in the imaginary part of the dielectric constants indicated that the VO₂(B) structure could perfectly absorb infrared light. The computed static dielectric constants with positive values, as derived from the optical properties, confirmed the conductivity of this material. Among the four proposed geometries of VO₂(B) in this study, the outcomes obtained by VO₂(B)_PPD reveal good results owing to the excellent consistency of its bandgap, magnetic and optical properties with other experimental and theoretical observations. The theoretical framework in our study will provide useful insight for future practical applications of the VO₂(B) polymorph in electronics and optoelectronics.