Assessment of the solvent effect on the organic reaction mechanisms through ab initio molecular dynamics simulations

• Grant number: 23/00531-8
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor
• Effective date (Start): May 15, 2023
• Effective date (End): May 14, 2024
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Claudio Francisco Tormena
• Grantee: Patrick Rodrigues Batista
• Supervisor: Barbara Kirchner
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Research place: Universität Bonn, Germany
• Associated to the scholarship: 21/09687-5 - Assessment of conformational preferences on fluorine-containing molecules and study of transmission pathway for JFH couplings using Car-Parrinello molecular dynamics, BP.PD

Abstract

Understanding the solvent effect on the chemical processes and reaction mechanisms is a hard task that has been intensively investigated for many years. Several experimental and theoretical studies have been showing how solvent dynamics dramatically change the reaction rate, yield, and selectivity. However, due to the computational treatment of explicit solvent molecules being difficult and time consuming, typically, the solvation energy of the solute is estimated by treating the solvent as a dielectric continuum. Thus, addressing the specific solute-solvent interactions, conformations, and entropic contributions that can alter the reaction path or lead to the high/small energy mechanism, are one major problem in computational chemistry. Given the challenges of modelingreaction mechanisms in solution, an ab initio investigation is proposed in this project, involving the modeling the explicit solvent-solute interactions and the way in which different solvents affect organic reaction mechanisms. For this, the most realistic theoretical method will be applied combining the ab initio molecular dynamics and metadynamics to better understand the bimolecularnucleophilic substitution (SN2) and bimolecular elimination (E2) reaction: CH3CH2Br + Cl- ’ CH3CH2Cl + CH2CH2 and also the Morita-Baylis-Hilman, which is an important method to form carbon-carbon chemical bonds. (AU)