Reactivity and Aromaticity: a Kohn-Sham Molecular Orbital Perspective.

• Grant number: 24/03646-3
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)
• Start date: September 01, 2024
• End date: August 31, 2025
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Ataualpa Albert Carmo Braga
• Grantee: Daniel Arley Santos Oliveira
• Supervisor: Friedrich Matthias Bickelhaupt
• Host Institution: Instituto de Química (IQ). Universidade de São Paulo (USP). São Paulo , SP, Brazil
• Institution abroad: University Amsterdam (VU), Netherlands
• Associated to the scholarship: 22/01685-6 - A Meta-Selective C-H Borylation and C-H Olefination by Noncovalent Interactions: Computational Study., BP.DD

Abstract

The Activation Strain Model (ASM) and Energy Decomposition Analysis (EDA) are fundamental methodologies rooted in and augmenting the Kohn Sham Molecular Orbital (KS-MO) Theory for understanding reactivity and diverse chemical phenomena. Their combined use allows the unraveling of the causal physical factors underlying the chemical phenomena of interest. These methods are based on the decomposition of the electronic energy along a reaction path into physically meaningful terms related to the deformations and interactions that occur along that path. In this project, we aim to employ the ASM in combination with the EDA to investigate two chemical processes. The first process is the competition between SN1 and SN2 nucleophilic substitution reactions, in which we will perform a systematic study on the effect of varying the nucleophiles, leaving groups, substrates, and reaction solvents. In the second research topic, we aim to extend the molecular orbital model for aromaticity developed by Prof. Dr. Matthias Bickelhaupt to a range of heterocyclic and inorganic benzene and cyclobutadiene analogs. In this context, acquiring in-depth knowledge and proficiency in the principles and application of ASM and EDA methodologies would be of fundamental importance for the candidate, as these two methodologies will certainly be useful in the original Ph.D. project.