Density-dependent onset of the long-range exchange: a key to donor-acceptor properties
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Date
2013-10-16
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American Chemical Society
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Abstract
Quantum mechanical methods based on the density functional theory (DFT) offer a realistic possibility of first-principles design of organic donor–acceptor systems and engineered band gap materials. This promise is contingent upon the ability of DFT to predict one-particle states accurately. Unfortunately, approximate functionals fail to align the orbital energies with ionization potentials. We describe a new paradigm for achieving this alignment. In the proposed model, an average electron-exchange hole separation controls the onset of the orbital-dependent exchange in approximate range-separated functionals. The correct description of one-particle states is thus achieved without explicit electron removal or attachment. Extensive numerical tests show that the proposed method provides physically sound orbital gaps and leads to excellent predictions of charge-transfer excitations and other properties critically depending on the tail of the electron density.