87543 20230914083231.0 doi 10.1039/c8cp07509c sideral 110844 ART-2019-110844 eng Munárriz, J. Universidad de Zaragoza (orcid)0000-0001-6089-6126 A first step towards quantum energy potentials of electron pairs 2019 Access copy available to the general public Unrestricted 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. info:eu-repo/grantAgreement/ES/MCIU/CTQ2015-65790-P info:eu-repo/grantAgreement/ES/MCIU/EST17-00161 info:eu-repo/grantAgreement/ES/MCIU/FPU14-06003 info:eu-repo/grantAgreement/ES/UZ-IBERCAJA-CAI/CB6-17 info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 3.43 2019 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL 8 / 37 = 0.216 2019 Q1 T1 CHEMISTRY, PHYSICAL 66 / 159 = 0.415 2019 Q2 T2 1.143 2019 Physics and Astronomy (miscellaneous) 2019 Q1 Physical and Theoretical Chemistry 2019 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Laplaza, R. Martín Pendás, A. Contreras-García, J. 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 21, 8 (2019), 4215-4223 Phys. chem. chem. phys. PHYSICAL CHEMISTRY CHEMICAL PHYSICS 1463-9076 698432 http://zaguan.unizar.es/record/87543/files/texto_completo.pdf Postprint 549624 http://zaguan.unizar.es/record/87543/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:87543 articulos driver 2023-09-13-10:44:36 ARTICLE