Application of density functional theory to study the electronic structure and magnetic behavior of clusters MPS (M = Fe, Co, Ni; n = 0 ~ 3).

Context: The article explores and compares the electronic structure and magnetic properties of transition metal phosphate materials, namely FePS, CoPS, and NiPS.

Research Findings: Analysis of the optimized configuration reveals significant insights into the electronic properties of MPS clusters. Electrons within the cluster exhibit a flow from the metal atom M and the non-metal atom P to the non-metal atom S. The S atom serves as the primary site for electrophilic reactions within the cluster, while the metal atom hosts the main site for nucleophilic reactions. Configurations 2a, 2b, 3a, 3b, and 3c exhibit enhanced electron mobility and optimal electronic properties. Moreover, the analysis of the magnetic properties of the optimized configurations demonstrates that the magnetic behavior of MPS clusters is influenced by the spin motion of α electrons in the p orbital. Metal atoms make a relatively significant contribution to the magnetic properties of MPS clusters. Configurations 1b, 2c, and 3a exhibit comparatively higher magnetic properties compared to other configurations of the same size. This study identifies the optimal configuration for the magnetic and electronic properties of transition metal phosphorothioate materials. It also elucidates the trends in magnetic and electronic properties as the number of metal atoms varies, thereby providing valuable theoretical support for the application of these materials in the fields of magnetic materials and electronic devices.

Methods: In this study, the Fe-based transition elements, namely Fe, Co, and Ni, are selected as the metal atoms M. The cluster MPS is used to simulate the local structure of the material, allowing for an investigation into the influence of the metal atoms on its electronic and magnetic properties. By increasing the number of metal atoms and expanding the cluster size, the variations in these properties are explored. Density functional theory (DFT) calculations are performed using the B3LYP functional within the Gaussian09 software package. The MPS cluster is subjected to optimal calculations and vibrational analysis at the def2-tzvp quantization level, resulting in optimized configurations with different spin multiplet degrees. Quantum chemistry software GaussView, wave function analysis software Multiwfn, and plotting software Origin are utilized for data characterization and graphical representation of the magnetic and electronic properties of the optimized configurations. Through the employment of these computational tools, valuable insights into the magnetic and electronic properties of the MPS cluster and its dependency on different metal atoms are obtained.