Study of direct methods in the determination of pKa and redox potentials for actinides

• Grant number: 23/02596-0
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• Start date: September 01, 2023
• End date: August 31, 2024
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Rogério Custodio
• Grantee: Felipe Ribeiro Dutra
• Supervisor: David Adams Dixon
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil
• Institution abroad: University of Alabama (UA), United States
• Associated to the scholarship: 21/03201-3 - Study of the direct method for calculating pKa for different multiprotic species from quantum calculations, BP.DR

Abstract

Recent studies have demonstrated the efficiency of methodologies that predict pKa directly in the aqueous phase, without the use of thermodynamic cycles. A preliminary alternative for pKa calculation based on the direct reaction was developed by the authors, demonstrating an excellent agreement between values calculated with electronic structure methods and experimental data. The present study intends to predict pKa's and redox potentials in systems containing actinides while evaluating the applicability and generalized nature of different direct schemes. It is intended to analyze electronic and structural effects at different levels of theory involving several quantum methods: density functional theory, composite methods (e.g., CBS-QB3, FPD), and correlation methods (e.g., CI, CCSD) allied to techniques that incorporate relativistic effects. The solvent effect will be evaluated using implicit solvation models (e.g., SMD, COSMO) and combinations of implicit models and explicit molecules by the supermolecule-continuum approach. (AU)