caa a22 4500 605488665 CHVBK 20210128100456.0 cr unu---uuuuu 210128e20151101xx s 000 0 eng 10.1007/s00214-015-1730-7 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1730-7 Insights into the chemical meanings of the reaction electronic flux [Elektronische Daten] [Christophe Morell, Vincent Tognetti, Emmanuelle Bignon, Elise Dumont, Noemi Hernandez-Haro, Barbara Herrera, André Grand, Soledad Gutiérrez-Oliva, Laurent Joubert, Alejandro Toro-Labbé, Henry Chermette] 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. Springer-Verlag Berlin Heidelberg, 2015 Conceptual DFT nationallicence Chemical potential nationallicence Reaction electronic flux nationallicence Spontaneous process nationallicence Morell Christophe Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Claude Bernard Lyon 1, 5 rue de la Doua, 69100, Villeurbanne, France aut Tognetti Vincent Normandy University, COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821, Mont St Aignan. Cedex, France aut Bignon Emmanuelle Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Claude Bernard Lyon 1, 5 rue de la Doua, 69100, Villeurbanne, France aut Dumont Elise Laboratoire de Chimie, UMR 5182, CNRS Ecole Normale Supérieure de Lyon, Lyon, France aut Hernandez-Haro Noemi CEA Grenoble -INAC/SCIB/LAN (UMR-E n°3 CEA-UJF), CEA-Grenoble, 17, rue des Martyrs, 38054, Grenoble Cedex 9, France aut Herrera Barbara Nucleus Millenium Chemical Processes and Catalysis (CPC), Laboratorio de Quimica Teorica Computacional (QTC), Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago, Chile aut Grand André CEA Grenoble -INAC/SCIB/LAN (UMR-E n°3 CEA-UJF), CEA-Grenoble, 17, rue des Martyrs, 38054, Grenoble Cedex 9, France aut Gutiérrez-Oliva Soledad Nucleus Millenium Chemical Processes and Catalysis (CPC), Laboratorio de Quimica Teorica Computacional (QTC), Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago, Chile aut Joubert Laurent Normandy University, COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821, Mont St Aignan. Cedex, France aut Toro-Labbé Alejandro Nucleus Millenium Chemical Processes and Catalysis (CPC), Laboratorio de Quimica Teorica Computacional (QTC), Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago, Chile aut Chermette Henry Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Claude Bernard Lyon 1, 5 rue de la Doua, 69100, Villeurbanne, France aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/11(2015-11-01), 1-7 1432-881X 134:11<1 2015 134 214 https://doi.org/10.1007/s00214-015-1730-7 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00214-015-1730-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Morell Christophe Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Claude Bernard Lyon 1, 5 rue de la Doua, 69100, Villeurbanne, France aut NATIONALLICENCE 700 1- Tognetti Vincent Normandy University, COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821, Mont St Aignan. Cedex, France aut NATIONALLICENCE 700 1- Bignon Emmanuelle Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Claude Bernard Lyon 1, 5 rue de la Doua, 69100, Villeurbanne, France aut NATIONALLICENCE 700 1- Dumont Elise Laboratoire de Chimie, UMR 5182, CNRS Ecole Normale Supérieure de Lyon, Lyon, France aut NATIONALLICENCE 700 1- Hernandez-Haro Noemi CEA Grenoble -INAC/SCIB/LAN (UMR-E n°3 CEA-UJF), CEA-Grenoble, 17, rue des Martyrs, 38054, Grenoble Cedex 9, France aut NATIONALLICENCE 700 1- Herrera Barbara Nucleus Millenium Chemical Processes and Catalysis (CPC), Laboratorio de Quimica Teorica Computacional (QTC), Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago, Chile aut NATIONALLICENCE 700 1- Grand André CEA Grenoble -INAC/SCIB/LAN (UMR-E n°3 CEA-UJF), CEA-Grenoble, 17, rue des Martyrs, 38054, Grenoble Cedex 9, France aut NATIONALLICENCE 700 1- Gutiérrez-Oliva Soledad Nucleus Millenium Chemical Processes and Catalysis (CPC), Laboratorio de Quimica Teorica Computacional (QTC), Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago, Chile aut NATIONALLICENCE 700 1- Joubert Laurent Normandy University, COBRA UMR 6014 & FR 3038, Université de Rouen, INSA Rouen, CNRS, 1 rue Tesniére, 76821, Mont St Aignan. Cedex, France aut NATIONALLICENCE 700 1- Toro-Labbé Alejandro Nucleus Millenium Chemical Processes and Catalysis (CPC), Laboratorio de Quimica Teorica Computacional (QTC), Facultad de Quimica, Pontificia Universidad Catolica de Chile, Santiago, Chile aut NATIONALLICENCE 700 1- Chermette Henry Université de Lyon, Institut des Sciences Analytiques, UMR 5280, CNRS, Université Claude Bernard Lyon 1, 5 rue de la Doua, 69100, Villeurbanne, France aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/11(2015-11-01), 1-7 1432-881X 134:11<1 2015 134 214