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Bonding description of the Harpoon mechanism

The lowest lying states of LiH have been widely used to develop and calibrate many different methods in quantum mechanics. In this paper, we show that the electron-transfer processes occurring in these two states are a difficult test for chemical bonding descriptors and can be used to assess new bonding descriptors on its ability to recognise the harpoon mechanism. To this aim, we study the bond formation mechanism in a series of diatomic molecules. In all studied electron reorganisation mechanisms, the maximal electron-transfer variation point along the bond formation path occurs when about half electron has been transferred from one atom to another. If the process takes place through a harpoon mechanism, this point of the reaction path coincides with the avoided crossing. The electron sharing indices and one-dimensional plots of the electron localisation function and the Laplacian of the electron density along the molecular axis can be used to monitor the bond formation in diatomics and provide a distinction between the harpoon mechanism and a regular electron reorganisation process

This research has been funded by the MINECO projects CTQ2014-52525-P and CTQ2014-54306-P, the Basque CountryConsolidatedGroup ProjectNo. IT588-13, the FEDER grant UNGI10-4E-801 (European Fund for Regional Development), the Generalitat de Catalunya (project number 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA 2014 prize to M.S.) and the predoctoral fellowship FPU13/00176. Excellent service by the Centre de Serveis Científics i Acadèmics de Catalunya (CESCA) and technical and human support provided by SGI/IZO-SGIker UPV/EHU are gratefully acknowledged

© Molecular Physics, 2016, vol. 114, núm. 7-8, p. 1345-1355

Taylor and Francis

Author: Rodríguez Mayorga, Mauricio
Ramos-Cordoba, Eloy
Salvador Sedano, Pedro
Solà i Puig, Miquel
Matito i Gras, Eduard
Date: 2016 April 17
Abstract: The lowest lying states of LiH have been widely used to develop and calibrate many different methods in quantum mechanics. In this paper, we show that the electron-transfer processes occurring in these two states are a difficult test for chemical bonding descriptors and can be used to assess new bonding descriptors on its ability to recognise the harpoon mechanism. To this aim, we study the bond formation mechanism in a series of diatomic molecules. In all studied electron reorganisation mechanisms, the maximal electron-transfer variation point along the bond formation path occurs when about half electron has been transferred from one atom to another. If the process takes place through a harpoon mechanism, this point of the reaction path coincides with the avoided crossing. The electron sharing indices and one-dimensional plots of the electron localisation function and the Laplacian of the electron density along the molecular axis can be used to monitor the bond formation in diatomics and provide a distinction between the harpoon mechanism and a regular electron reorganisation process
This research has been funded by the MINECO projects CTQ2014-52525-P and CTQ2014-54306-P, the Basque CountryConsolidatedGroup ProjectNo. IT588-13, the FEDER grant UNGI10-4E-801 (European Fund for Regional Development), the Generalitat de Catalunya (project number 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA 2014 prize to M.S.) and the predoctoral fellowship FPU13/00176. Excellent service by the Centre de Serveis Científics i Acadèmics de Catalunya (CESCA) and technical and human support provided by SGI/IZO-SGIker UPV/EHU are gratefully acknowledged
Format: application/pdf
ISSN: 0026-8976
Document access: http://hdl.handle.net/10256/13705
Language: eng
Publisher: Taylor and Francis
Collection: MINECO/PN 2011-2015/CTQ2014-52525-P
MINECO/PE 2015-2017/CTQ2014-54306-P
Reproducció digital del document publicat a: http://dx.doi.org/10.1080/00268976.2015.1121297
Articles publicats (D-Q)
Is part of: © Molecular Physics, 2016, vol. 114, núm. 7-8, p. 1345-1355
Rights: Tots els drets reservats
Subject: Enllaços químics
Chemical bonds
Química de l’estat excitat
Excited state chemistry
Title: Bonding description of the Harpoon mechanism
Type: info:eu-repo/semantics/article
Repository: DUGiDocs

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