Electronic and spectral properties of ametal-organic super container molecule by single point DFT

Metal-organic super container (MOSC) molecules are ideal candidates for photocatalysis due to their construction with transition metal centres and tuneable cavity sizes that could house catalytic sites. The basic electronic structure for a model of extremely large size (more than 2000 ions) is explored by single point calculation using unrestricted density functional theory, and Perdue–Burke–Ernzerhof functional in Vienna ab initio simulation package software. The information obtained through these calculations (such as density of states, absorbance spectra, and charge density) will allow for analysis of a MOSC's catalytic ability. Electronic characteristics of the nanostructures (MOSCs and their building blocks) in the ground and photoexcited electronic configurations are examined. We explore if the presence of transition metal ions with open shells in such close proximity to one another may result in high spin configurations and show any arrangement into ferromagnetic ordering. Spin-unrestricted computation was applied to evaluate how optical properties could be affected by d–d transitions. A scan of a spin-polarisation parameter allows one to resolve spin configuration and obtain a connection between theory and experiment. Analysis of Kohn–Sham orbitals of interest provides insight into charge transfer mechanisms, which were found to contribute to multiple low-energy charge transfer states to the electronic structure.