2015/10/31 by Mauricio Rodriguez-Mayorga, Mauricio Rodríguez‐Mayorga, Eloy Ramos‐Cordoba +5 · 1 citation
Chemistry · Engineering · Physics and Astronomy · #Chemical physics #Chemistry #Computational chemistry #Epistemology #Force Microscopy Techniques and Applications #Mechanical Engineering and Vibrations Research #Mechanism (biology) #Organic Chemistry Cycloaddition Reactions #Philosophy #physics.chem-ph
paper · pdf · doi:10.1080/00268976.2015.1121297
published as Mol. Phys. 114, 1345 (2016) · 21 pages, 9 figures
arxiv created 2015/11/11 · openalex publication_date 2015/12/16 · arxiv updated 2017/11/16 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05
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.