Solvent effect in NMR parameters by ab initio molecular dynamics
| Grant number: | 19/18727-0 |
| Support type: | Scholarships in Brazil - Doctorate (Direct) |
| Effective date (Start): | November 01, 2019 |
| Effective date (End): | July 31, 2023 |
| Field of knowledge: | Physical Sciences and Mathematics - Chemistry - Physical-Chemistry |
| Principal Investigator: | Lucas Colucci Ducati |
| Grantee: | Leonardo Araujo Schenberg |
| Home Institution: | Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil |
Abstract The study of the water solvation effect and especially the solvent coordination, on the shielding tensor/chemical shift and indirect spin-spin coupling constants of 199Hg in biomolecule adducts will be targeted. These complexes have a strong solvent influence, requiring the use of explicit solvation and a dynamic description of the solute-solvent system. These mercury adducts are still studied nowadays due to their large toxicological effects and environmental contamination. However, the theoretical values of magnetic parameters with static geometries at DFT level with the implicit solvent effect and relativistic Hamiltonian overestimate the experimental values by about 50%. The poor description of the electronic structure of the 199Hg adducts of biomolecules in static models reflected in the low accuracy of the calculated NMR properties demands a better description of the magnetic properties by dynamic models. Therefore, the Kohn-Sham (KS) Car-Parrinello (CPMD) molecular dynamics and hybrid KS calculations of magnetic properties, with and without solvent effect, will be used. This new approach, combining KS-CPMD and hybrid KS-DFT calculations for magnetic properties determination, has been proposed and developed recently and has been successfully applied to Tl-Pt and Pt-Pt dinuclear transition metal compounds. (AU) | |