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Scopes and Limitations of DFT Methods for Accurate Spectroscopic Prediction of Systems with Intramolecular Hydrogen Bonds

Publication Date
Authors
Author Name
Milagros Amichetti
Author Organization
Instituto de Química de Rosario. Universidad Nacional de Rosario.
Author Name
Maria Marta Zanardi
Author Organization
Instituto de Investigaciones en Ingeniería Ambiental, Química y Biotecnología Aplicada (INGEBIO). Facultad de Química e Ingeniería del Rosario, Pontificia Universidad Católica Argentina
Author Name
Ariel Sarotti
Author Organization
Instituto de Química de Rosario. Universidad Nacional de Rosario.

The application of quantum-based NMR methods for the structural elucidation of natural and unnatural products has grown significantly. However, accurately calculating the conformational landscape of flexible molecules with intricate intramolecular hydrogen bonding (IHB) networks continues to be a major challenge. Previous studies have shown that to solve biased systems with strong IHB interactions, it is necessary to calculate the Boltzmann contributions using Gibbs free energies computed with at least a triple-ξ basis set and the SMD solvation model. In this work, we thoroughly studied the effect of entropic contributions (through Gibbs free energy calculations) on the performance of DP4+, a chemoinformatics tool designed for in silico structural elucidation. 

The goal is to advance the development of computational methodologies that accurately describe systems with IHB, improving the prediction of molecular properties for these systems while contributing to sustainability. By utilizing these methodologies, the traditionally negative impact of experimental chemistry is reduced, minimizing the use of reagents, solvents, and energy, while promoting the exploration of new molecules and materials with lower environmental and economic costs.

 

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XXIV National Symposium of Organic Chemistry, Argentina.
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