Study of chloroform solvent effect on 199Hg NMR properties of methylmercury derivatives by ab initio molecular dynamics and relativistic calculations

• Grant number: 22/10688-9
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)
• Effective date (Start): January 15, 2023
• Effective date (End): January 14, 2024
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Lucas Colucci Ducati
• Grantee: Leonardo Araujo Schenberg
• Supervisor: Jochen Autschbach
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Research place: State University of New York, Buffalo State (SUNY), United States
• Associated to the scholarship: 19/18727-0 - Study of 199Hg organometallic compounds in solution by ab initio molecular dynamics and relativistic NMR calculations, BP.DD

Abstract

The study of the solvation effect of chloroform, and mainly of the solvent coordination, on the spin-spin indirect coupling constants (J) of 199Hg in CH3-Hg-X, where X={CH3, Cl, Br, I}, will be studied. These complexes have a strong influence of the solvent, requiring the use of explicit solvation and a dynamic description of the solute-solvent system. These mercury complexes have been studied due to their high toxicological effects and environmental contamination. However, the theoretical predictions of the magnetic parameters at the DFT level, with static geometries, the implicit solvent effect, and relativistic corrections, still underestimate the experimental values by about 21 to 35%. The poor description of the electronic structure of the 199Hg complexes in solution obtained by the static models, makes dynamic models necessary for better description of electron density at 199Hg nucleus and its M-L bonds, as well as NMR properties. For this aim, Kohn-Sham (KS) Car-Parrinello (CPMD) molecular dynamics and relativistic hybrid KS-DFT calculations of magnetic properties will be applied. (AU)