| Texto completo | |
| Autor(es): |
Sauza-de la Vega, Arturo
;
Duarte, Leonardo J.
;
Silva, Arnaldo F.
;
Skelton, Jonathan M.
;
Rocha-Rinza, Tomas
;
Popelier, Paul L. A.
Número total de Autores: 6
|
| Tipo de documento: | Artigo Científico |
| Fonte: | Physical Chemistry Chemical Physics; v. 24, n. 18, p. 17-pg., 2022-04-28. |
| Resumo | |
Understanding and controlling polymorphism in molecular solids is a major unsolved problem in crystal engineering. While the ability to calculate accurate lattice energies with atomistic modelling provides valuable insight into the associated energy scales, existing methods cannot connect energy differences to the delicate balances of intra- and intermolecular forces that ultimately determine polymorph stability ordering. We report herein a protocol for applying Quantum Chemical Topology (QCT) to study the key intra- and intermolecular interactions in molecular solids, which we use to compare the three known polymorphs of succinic acid including the recently-discovered gamma form. QCT provides a rigorous partitioning of the total energy into contributions associated with topological atoms, and a quantitative and chemically intuitive description of the intra- and intermolecular interactions. The newly-proposed Relative Energy Gradient (REG) method ranks atomistic energy terms (steric, electrostatic and exchange) by their importance in constructing the total energy profile for a chemical process. We find that the conformation of the succinic acid molecule is governed by a balance of large and opposing electrostatic interactions, while the H-bond dimerisation is governed by a combination of electrostatics and sterics. In the solids, an atomistic energy balance emerges that governs the contraction, towards the equilibrium geometry, of a molecular cluster representing the bulk crystal. The protocol we put forward is as general as the capabilities of the underlying quantum-mechanical model and it can provide novel perspectives on polymorphism in a wide range of chemical systems. (AU) | |
| Processo FAPESP: | 18/24844-7 - Uso de tensores polares atômicos e parâmetros QCT para treinar um modelo de machine learning e prever constantes de Hammett |
| Beneficiário: | Leonardo José Duarte |
| Modalidade de apoio: | Bolsas no Exterior - Estágio de Pesquisa - Doutorado Direto |
| Processo FAPESP: | 17/22741-3 - Uso de multipolos atômicos e desenvolvimento de modelos de machine learning na investigação de estados de transição |
| Beneficiário: | Leonardo José Duarte |
| Modalidade de apoio: | Bolsas no Brasil - Doutorado Direto |
| Processo FAPESP: | 15/22247-3 - Utilizando a teoria quantum chemical Topology para a modelagem de campos de força para peptídeos através de densidades eletrônicas |
| Beneficiário: | Arnaldo Fernandes da Silva Filho |
| Modalidade de apoio: | Bolsas no Exterior - Estágio de Pesquisa - Pós-Doutorado |
| Processo FAPESP: | 14/21241-9 - Inclusão de polarização na descrição de aminoácidos e peptídeos utilizando multipolos atômicos calculados a partir de densidades eletrônicas |
| Beneficiário: | Arnaldo Fernandes da Silva Filho |
| Modalidade de apoio: | Bolsas no Brasil - Pós-Doutorado |