| Full text | |
| Author(s): |
Sauza-de la Vega, Arturo
;
Duarte, Leonardo J.
;
Silva, Arnaldo F.
;
Skelton, Jonathan M.
;
Rocha-Rinza, Tomas
;
Popelier, Paul L. A.
Total Authors: 6
|
| Document type: | Journal article |
| Source: | Physical Chemistry Chemical Physics; v. 24, n. 18, p. 17-pg., 2022-04-28. |
| Abstract | |
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) | |
| FAPESP's process: | 18/24844-7 - Using atomic polar tensors and QCT parameters to train a machine learning model and predict Hammett constants. |
| Grantee: | Leonardo José Duarte |
| Support Opportunities: | Scholarships abroad - Research Internship - Doctorate (Direct) |
| FAPESP's process: | 17/22741-3 - Using atomic multipoles and developing machine learning models to investigate transition states |
| Grantee: | Leonardo José Duarte |
| Support Opportunities: | Scholarships in Brazil - Doctorate (Direct) |
| FAPESP's process: | 15/22247-3 - Using the Quantum Chemical Topology theory for modeling force fields for peptides using electron densities |
| Grantee: | Arnaldo Fernandes da Silva Filho |
| Support Opportunities: | Scholarships abroad - Research Internship - Post-doctor |
| FAPESP's process: | 14/21241-9 - The inclusion of polarization effects in the description of amino acids and peptides through the use of atomic multipoles obtained from electron densities |
| Grantee: | Arnaldo Fernandes da Silva Filho |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |