Journal
JOURNAL OF COMPUTATIONAL CHEMISTRY
Volume 37, Issue 19, Pages 1794-1800Publisher
WILEY
DOI: 10.1002/jcc.24394
Keywords
denisty functional theory; electronic chemical potential; conceptual DFT; reaction electronic flux; symmetry
Categories
Funding
- Inicitiva Cientifica Milenio [N 120082]
- FONDECYT [N 1130072, N 3150542]
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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-defined reaction electronic flux (REF) profile, since it is defined as the derivative of the chemical potential with respect to the reaction coordinate. To overcome this deficiency, we propose a new way for the calculation of the chemical potential based on a many orbital approach, suitable for reactions in which symmetry is preserved. This new approach gives rise to a new descriptor: symmetry adapted chemical potential (SA-CP), which is the chemical potential corresponding to a given irreducible representation of a symmetry group. A corresponding symmetry adapted reaction electronic flux (SA-REF) is also obtained. Using this approach smooth chemical potential profiles and well defined REFs are achieved. An application of SA-CP and SA-REF is presented by studying the C-s enol-keto tautomerization of thioformic acid. Two SA-REFs are obtained, JA() and JA (). It is found that the tautomerization proceeds via an in-plane delocalized 3-center 4-electron O-H-S hypervalent bond which is predicted to exist only in the transition state (TS) region. (c) 2016 Wiley Periodicals, Inc.
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