Abstract
DFT-D3 and TD-DFT calculations at B3LYP/6-311 + g(d) level of theory are employed to study the influence of the TM (Co and Ni) doping, the adsorption of CH3OH, and the external electric field (EF) on the electronic and optical properties of B12N12. The results are analyzed in point of view of BSSE corrected adsorption energies, the density of states (DOS), NBO atomic charges, and UV-vis spectra. The obtained values of dipole moment, ionization potential, chemical potential, hardness, and electrophilicity verified that the doped TM-boron nitride nano-cages are more reactive than the pure B12N12 nano-cage as well the TMB11N12 nano-cages are more reactive than TMB12N11 nano-cages. Additionally, the doping decreases the HOMO-LUMO gap energy gap to 55% and 30% and enhances the adsorption energy by 41.4% and 44.1% for CoB11N12 and NiB11N12 nano-cages, respectively. The adsorption of CH3OH reduces the HOMO-LUMO gap for the B12N12 and enlarge that for the TMB11N12. The value and the direction of the applied EF control the adsorption energy, sensitivity, response time, and recovery time. The TD-DFT calculations declare that the CH3OH adsorption on CoB11N12 and NiB11N12 under the influence of the EF causes considerable shifts for the lambda(max) value in the visible region. Thus, the obtained results may be fruitful for designing an electrical and optical sensor for CH3OH utilizing pure and doped boron nitride nano-cages.