Computational Insights into the Role of the Frontiers Orbital in the Chemistry of Tridentate Ligands

Abstract

The FERM O concept emerges as a powerful and innovative implement to investigate the role of molecular orbitals applied in the description of breakage and formation of chemical bonds. In this work, Hartree-Fock (HF) and Density Functional Theory (DFT) calculations were carried out for a series of four tridentate ligands and their behavior was analyzed using molecular orb ital (M O) energies. It was observed that HOMO energies are inadequate to describe the Pearson´s Hard and Solf acid-base (HSA B) p ricinple behavior of these compounds. By using the frontier effective-for-reaction molecular orbital (FERM O) concept, the reactions that are driven by HOM O, and those that are not, can be better exp lained, independent of the calculation method used, since both HF and Kohn-Sham methodologies lead to the same FERM O.

A DFT Study of Structural and Electronic Properties of ZnS Polymorphs and its Pressure‐Induced Phase Transitions

“…Theoretical and computational studies, based on the Density Functional Theory (DFT) have emerged to provide important information regarding the electronic and structural properties of solid materials and molecules, and have shown great value, not only in the in interpretation of experiments, but also in the prediction of important aspects of new properties and in the design of new devices. Nevertheless, despite the recent improvements in DFT, there are still difficulties in using DFT to properly describe van der Waals interactions (dispersion) and charge‐transfer excitations due to the lack of exact Hartree–Fock exchange in some functionals . To overcome these limitations, an empirical correction to include dispersion interactions in DFT methods has been proposed by Grimme .…”

Ball milling: a green mechanochemical approach for synthesis of Ni (II), Co (II) and Cu (II) complexes

“… The bond angles of the diketone unit of HD 1 , HD 2 and HD 3 changed somewhat upon coordination that increased or decreased on complexation because of bonding The bond lengths of all active groups’ participation in coordination are longer than that of the ligand . All bond lengths associate with the empirical IR frequencies, whereas the trial IR frequency values require lower energy of vibration. …”

PRIMoRDiA: A Software to Explore Reactivity and Electronic Structure in Large Biomolecules

“…For small molecules with significant degeneracy, some approaches were already proposed, such as an earlier visualization of the MO to choose those most suited for the reaction under scrutiny, which is not practical for large systems. Some studies indicated the need of calculating the Fukui function as an average over the degenerated states, and Pino-Rios and coworkers established an energy-weighted left Fukui function ( f – ).…”