Insights into the chemical meanings of the reaction electronic flux
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The negative derivative of the chemical potential with respect to the reaction coordinate is called reaction electronic flux and has recently focused a wide interest to better understand chemical reactions at molecular level. After much consideration, it is now well accepted that positive REF values are associated with spontaneous processes, while negative REF ones translate unspontaneous phenomena. These characteristics of the REF are based on a thermodynamic analogy and have been shown right through computational results. In this paper, we develop two analytical expressions of the REF in both the canonical and the grand canonical ensembles. The connection between both equations is established. They are then analyzed, and some arguments are put forward to support the alleged characteristic of the REF and its ability to properly discriminate spontaneous from unspontaneous phenomena.
KeywordsConceptual DFT Chemical potential Reaction electronic flux Spontaneous process
The research benefited from the support of Aviesan ITMO Cancer within the ‘‘Cancer Plan 2009–2013’’ and the application of Action 3.3. CM, AG, HC, ATL, BH and SG-O thank the joint program ECOS-CONICYT through action project ECOS No. C11E03. V.T. and L.J. gratefully acknowledge the Centre National de la Recherche Scientifique (CNRS) for a “Chaire d’Excellence” at the University of Rouen, the LABEX SynOrg for funding, and the CRIHAN computational centre for providing computational resources. HC acknowledges the GENCI/CINES for HPC resources/computer time (Project cpt2130). ATL, BH, SG-O acknowledge Project Nucleus Millenium CPC: ICM No. 120082 and Projects FONDECYT Nos. 1120093, 1130072 and 1141098.
- 7.Gázquez JL (2008) Perspectives on the density functional theory of chemical reactivity. J Mex Chem Soc 52:3–10Google Scholar
- 9.Anderson JSM, Melin J, Ayers PW (2007) Conceptual density-functional theory for general chemical reactions, including those that are neither charge- nor frontier-orbital-controlled. 1. Theory and derivation of a general-purpose reactivity indicator. J Chem Theory Comput 3:358–374CrossRefGoogle Scholar
- 36.Flores-Morales P, Gutiérrez-Oliva S, Silva E, Toro-Labbé A (2010) The reaction electronic flux: a new descriptor of the electronic activity taking place during a chemical reaction. Application to the characterization of the mechanism of the Schiff’s base formation in the Maillard reaction. J Mol Struct Theochem 943:121–126CrossRefGoogle Scholar