Theoretical studies of the first-row transition metal phosphides

The electronic structures and spectroscopic parameters of the ground and some low-lying excited states of the first-row transition metal phosphides have been calculated with the density functional theory using the Becke three-parameter hybrid exchange functional with the Lee-Yang-Parr correlation functional (B3LYP). The ground states of the transition metal phosphides are found to be (1)Sigma(+) (ScP), (2)Delta (TiP), (3)Delta (VP), (4)Sigma(-) (CrP), (5)Pi (MnP), (6)Sigma(+) (FeP), (5)Delta (CoP), (4)Delta (NiP), and (3)Sigma(-) (CuP). The B3LYP functional predicts an increase in covalent character in the bonds between the metal and the phosphorus across the transition metal series. The energies of the low-lying excited states relative to the ground state for TiP, FeP, and CoP have been found to be so small that many low-lying states are possible candidates to be the ground state. (C) 2003 American Institute of Physics.