Chemical potential and reaction electronic flux in symmetry controlled reactions

• Published in: Journal of computational chemistry Vol. 37; no. 19; pp. 1794 - 1800
• Main Authors: Vogt-Geisse, Stefan, Toro-Labbé, Alejandro
• Format: Journal Article
• Language: English
• Published: United States Blackwell Publishing Ltd 15.07.2016; Wiley Subscription Services, Inc
• Subjects: Approximation; Chemical bonds; Chemical reactions; conceptual DFT; denisty functional theory; electronic chemical potential; reaction electronic flux; Symmetry; denisty functional theory; conceptual DFT; symmetry; reaction electronic flux; electronic chemical potential
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.24394

In symmetry controlled reactions, orbital degeneracies among orbitals of different symmetries can occur along a reaction coordinate. In such case Koopmans' theorem and the finite difference approximation provide a chemical potential profile with nondifferentiable points. This results in an ill‐...