| Full text | |
| Author(s): |
Total Authors: 3
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| Affiliation: | [1] MIB, 131 Princess St, Manchester M1 7DN, Lancs - England
[2] Univ Manchester, Dept Chem, Oxford Rd, Manchester M13 9PL, Lancs - England
[3] Univ Estadual Campinas, Inst Quim, CP 6154, BR-13083970 Campinas, SP - Brazil
Total Affiliations: 3
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| Document type: | Review article |
| Source: | STRUCTURAL CHEMISTRY; v. 31, n. 2 FEB 2020. |
| Web of Science Citations: | 0 |
| Abstract | |
The quantum topological energy partitioning method Interacting Quantum Atoms (IQA) has been applied for over a decade resulting in an enlightening analysis of a variety of systems. In the last three years we have enriched this analysis by incorporating into IQA the two-particle density matrix obtained from Moller-Plesset (MP) perturbation theory. This work led to a new computational and interpretational tool to generate atomistic electron correlation and thus topologically based dispersion energies. Such an analysis determines the effects of electron correlation within atoms and between atoms, which covers both bonded and non-bonded ``through -space{''} atom-atom interactions within a molecule or molecular complex. A series of papers published by us and other groups shows that the behavior of electron correlation is deeply ingrained in structural chemistry. Some concepts that were shown to be connected to bond correlation are bond order, multiplicity, aromaticity, and hydrogen bonding. Moreover, the concepts of covalency and ionicity were shown not to be mutually excluding but to both contribute to the stability of polar bonds. The correlation energy is considerably easier to predict by machine learning (kriging) than other IQA terms. Regarding the nature of the hydrogen bond, correlation energy presents itself in an almost contradicting way: there is much localized correlation energy in a hydrogen bond system, but its overall effect is null due to internal cancelation. Furthermore, the QTAIM delocalization index has a connection with correlation energy. We also explore the role of electron correlation in protobranching, which provides an explanation for the extra stabilization present in branched alkanes compared to their linear counterparts. We hope to show the importance of understanding the true nature of the correlation energy as the foundation of a modern representation of dispersion forces for ab initio, DFT, and force field calculations. (AU) | |
| 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 |
| 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: | 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) |