Density functional theory study on interatomic forces and electronic properties of ConMoP(n = 1 ~ 5) cluster

Abstract

AbstractTo delve into the microscopic property variations of the ConMoP(n = 1 ~ 5) cluster, this study employs density functional theory at the B3LYP/def2‐TZVP quantum chemistry level. The paper conducts a comprehensive theoretical analysis of the clusters, examining parameters such as bond lengths, bond angles, electronic localization function (ELF), interaction region indicator function (IRI), independent gradient model based on the Hirshfeld partition, deformation density, electronic space range, chemical hardness and softness, polarizability, and dipole moment. The optimization process reveals 16 stable configurations for the ConMoP(n = 1 ~ 5) cluster, predominantly taking on a steric form. As the cluster size increases, the electronic delocalization of Co atoms intensifies, while the electronic properties of Mo atoms remain relatively stable. Notably, P atoms maintain a high degree of electronic delocalization. The interatomic forces within the clusters predominantly exhibit covalent bonding, with no evident repulsive effects observed between atoms. The bonding between metal atoms in the clusters leans toward a preference for covalent interaction. The degree of dispersion in the clusters increases with their growth, particularly evident in configuration 5‐a, which displays a broader spatial distribution. Configuration 3‐a demonstrates the most favorable activity, showcasing a relatively stable structure. Overall, configuration 3‐a emerges as a focal point for catalytic reactions. This article provides a more comprehensive analysis of the ConMoP(n = 1 ~ 5) cluster, yielding diverse results and enhancing the theoretical understanding of this cluster.