Study of 199Hg organometallic compounds in solution by ab initio molecular dynamics and relativistic NMR calculations

• Grant number: 19/18727-0
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• Start date: November 01, 2019
• End date: July 31, 2024
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Lucas Colucci Ducati
• Grantee: Leonardo Araujo Schenberg
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Associated scholarship(s): 22/10688-9 - Study of chloroform solvent effect on 199Hg NMR properties of methylmercury derivatives by ab initio molecular dynamics and relativistic calculations, BE.EP.DD

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)

Scientific publications

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

OBEID, GUILHERME; MORAES, GUSTAVO O.; PENNA, TATIANA C.; SCHENBERG, LEONARDO A.; DUCATI, LUCAS C.; CORRERA, THIAGO C.. Solvation effects on glyphosate protonation and deprotonation states evaluated by mass spectrometry and explicit solvation simulations. Journal of Chemical Physics, v. 158, n. 5, p. 12-pg., 2023-02-07. (20/10246-0, 19/12808-9, 17/20262-0, 17/17750-3, 15/08539-1, 19/18727-0, 19/25634-9, 20/08894-4, 21/06726-0, 14/15962-5)

ABDULLAYEV, YUSIF; KARIMOVA, NAZANI; SCHENBERG, LEONARDO A.; DUCATI, LUCAS C.; AUTSCHBACH, JOCHEN. Computational predictions on Bronsted acidic ionic liquid-catalyzed carbon dioxide conversion to five-membered heterocyclic carbonyl derivatives. Physical Chemistry Chemical Physics, v. 25, n. 12, p. 7-pg., 2023-02-23. (19/18727-0)