This work presents a relativistic calculation of electron delocalization, optical properties, and zero field splitting in a group of molecules with the structure (C 8H 8)M(μ 2-,η 8= C 8H 8)M(C 8H 8), where M = Ti, Zr and Th. Additionally we also studied the heterobimetallic combinations (Ti-Th and Zr-Th). The molecular properties are discussed based on their electronic structure and the influence of the electron mobility in metal-metal communication. Nucleus independent chemical shift (NICS) was determined via the gauge-including-atomic-orbital (GIAO) method with the OPBE functional. The time-dependent density functional theory (TDDFT) was employed to calculate excitation energies, and the electronic transitions over 500 nm are presented with the objective to analyze the transition metal role as an antenna effect in the absorption band in the near-IR region. Finally the ZFS was calculated using Pederson-Khana and coupled perturbed DFT approaches implemented in the ORCA code. The contributions to spin-spin coupling (SS) and spin-orbit coupling (SOC) were analyzed, and the spin-density over the metal centers is discussed employing our scheme of metal-metal communication. Our aim is to determine the influence of the electronic structure over the optical and magnetic properties in a group of model compounds to understand the transition metals effect over these properties.
Áreas temáticas de ASJC Scopus
- Química física y teórica