MP2-IQA: upscaling the analysis of topologically partitioned electron correlation

Autor(es)

Silva, Arnaldo F. ^[1] ; Popelier, Paul L. A. ^{[2, 3]}

Afiliação do(s) autor(es)

^[1] Univ Estadual Campinas, Inst Quim, BR-13083970 Campinas, SP - Brazil

^[2] Univ Manchester, Manchester Inst Biotechnol, 131 Princess St, Manchester M1 7DN, Lancs - England

^[3] Univ Manchester, Sch Chem, Oxford Rd, Manchester M13 9PL, Lancs - England

• Tipo de documento: Artigo Científico
• Fonte: Journal of Molecular Modeling; v. 24, n. 8 AUG 2018.
• Citações Web of Science: 2

Resumo

When electronic correlation energy is partitioned topologically, a detailed picture of its distribution emerges, both within atoms and between any two atoms. This methodology allows one to study dispersion beyond its more narrow definition in long-range Rayleigh-Schrodinger perturbation theory. The interacting quantum atoms (IQA) method was applied to MP2/6-31G(d,p) (uncontracted) wave functions of a wide variety of systems: glycineaEuro broken vertical bar water (hydration), the ethene dimer (pi-pi interactions), benzene (aromaticity), cyclobutadiene (antiaromaticity), and NH3BH3 (dative bond). Through the study of molecular complexes it turns out that dispersion energy is either important to a system's stabilization (for the C2H4 dimer) or not important (for GlyaEuro broken vertical bar H2O). We have also discovered that the delocalization in benzene lowers the strength of Coulomb repulsion in the bonds, which has been quantified for the first time through IQA. Finally, we showed that the nature of the dative bond is much different from that of a regular covalent bond as it is not destabilized by electronic correlation. Finally, the conclusions obtained for these archetypical systems have implications for the future of the quantum topological force field FFLUX in the simulation of larger systems. (AU)

• 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
• 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