Abstract: In order to find out the influence of the hybridization of Fe and P atoms on the stability of Fe₄P clusters and the relationship between the polarizability and the stability of the optimized configurations, according to the density functional theory and the principle of topology, a total of 16 initial configurations of Fe₄P in binary and quadruple states are designed under B3LYP/lanl2dz high quantum chemistry level chemical configuration. The polarizability and density of states of eight configurations are studied, and the following conclusions are drawn: configuration 5⁽⁴⁾ has the largest anisotropy invariant, which has the strongest response to the external field and is easily affected by the external field; configuration 2⁽²⁾ has the largest polarizability and the largest degree of deformation; configuration 2⁽⁴⁾ has the smallest value of polarizability, which is the least prone to deformation, and it also shows that the multiplicity will affect the polarizability of the response configuration to a certain extent. There are five main hybridization modes of Fe—P bond, which are p-p, p-d, p-p-d, p-d-d and s-s-p-p, and the p-d and p-p-d hybridizations play an important role in promoting the stability of Fe—P bond in cluster Fe₄P.

Key words: cluster Fe₄P, density functional theory, polarizability, density of states, hybridization