A first step towards quantum energy potentials of electron pairs

Munárriz, J. (Universidad de Zaragoza) ; Laplaza, R. ; Martín Pendás, A. ; Contreras-García, J.

Resumen: A first step towards the construction of a quantum force field for electron pairs in direct space is taken. Making use of topological tools (Interacting Quantum Atoms and the Electron Localisation Function), we have analysed the dependency of electron pairs electrostatic, kinetic and exchange-correlation energies upon bond stretching. Simple correlations were found, and can be explained with elementary models such as the homogeneous electron gas. The resulting energy model is applicable to various bonding regimes: from homopolar to highly polarized and even to non-conventional bonds. Overall, this is a fresh approach for developing real space-based force fields including an exchange-correlation term. It provides the relative weight of each of the contributions, showing that, in common Lewis structures, the exchange correlation contribution between electron pairs is negligible. However, our results reveal that classical approximations progressively fail for delocalised electrons, including lone pairs. This theoretical framework justifies the success of the classic Bond Charge Model (BCM) approach in solid state systems and sets the basis of its limits. Finally, this approach opens the door towards the development of quantitative rigorous energy models based on the ELF topology.

Idioma: Inglés

DOI: 10.1039/c8cp07509c

Año: 2019

Publicado en: PHYSICAL CHEMISTRY CHEMICAL PHYSICS 21, 8 (2019), 4215-4223
ISSN: 1463-9076

Factor impacto JCR: 3.43 (2019)

Categ. JCR: PHYSICS, ATOMIC, MOLECULAR & CHEMICAL rank: 8 / 37 = 0.216 (2019) - Q1 - T1
Categ. JCR: CHEMISTRY, PHYSICAL rank: 66 / 159 = 0.415 (2019) - Q2 - T2

Factor impacto SCIMAGO: 1.143 - Physics and Astronomy (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/MCIU/CTQ2015-65790-P
Financiación: info:eu-repo/grantAgreement/ES/MCIU/EST17-00161
Financiación: info:eu-repo/grantAgreement/ES/MCIU/FPU14-06003
Financiación: info:eu-repo/grantAgreement/ES/UZ-IBERCAJA-CAI/CB6-17

Tipo y forma: Article (PostPrint)

Área (Departamento): Área Química Física (Dpto. Química Física)