The crystal structure, band structure, density of states, Mulliken charge, bond population and optical properties for LiBi_(1-x)M_xO_3(M=V, Nb, and Ta) were investigated using hybrid density functional theory. It was found that LiBiO_3 doped with V, Nb, and Ta presented distinctly stronger covalent interactions in M-O(M=V, Nb, and Ta) than Bi-O, thus resulting in mild distortion of the structure and facilitating the separation of photogenerated carriers. Furthermore, the hybridizations of Bi-6s, M-d(M=V, Nb, and Ta) and O-2p widened the valence and conduction bands, which promoted transmission of photogenerated carriers in the band edge and thus caused better photocatalytic performance.
