Journal Article10.1063/1.2360263
Extracting electron transfer coupling elements from constrained density functional theory.
Qin Wu,Troy Van Voorhis +1 more
341
TL;DR: A method is presented for calculating the electronic coupling matrix element (Hab) based on constrained DFT and completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases.
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Abstract: Constrained density functional theory (DFT) is a useful tool for studying electron transfer (ET) reactions. It can straightforwardly construct the charge-localized diabatic states and give a direct measure of the inner-sphere reorganization energy. In this work, a method is presented for calculating the electronic coupling matrix element (Hab) based on constrained DFT. This method completely avoids the use of ground-state DFT energies because they are known to irrationally predict fractional electron transfer in many cases. Instead it makes use of the constrained DFT energies and the Kohn-Sham wave functions for the diabatic states in a careful way. Test calculations on the Zn2+ and the benzene-Cl atom systems show that the new prescription yields reasonable agreement with the standard generalized Mulliken-Hush method. We then proceed to produce the diabatic and adiabatic potential energy curves along the reaction pathway for intervalence ET in the tetrathiafulvalene-diquinone (Q-TTF-Q) anion. While the u...
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Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
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