Ionization Energies, Electron Affinities, and Polarization Energies of Organic Molecular Crystals: Quantitative Estimations from a Polarizable Continuum Model (PCM)–Tuned Range-Separated Density Functional Approach

Haitao Sun, Sean Ryno, Cheng Zhong, Mahesh Kumar Ravva, Zhenrong Sun, Thomas Körzdörfer, Jean-Luc Bredas

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We propose a new methodology for the first-principles description of the electronic properties relevant for charge transport in organic molecular crystals. This methodology, which is based on the combination of a non-empirical, optimally tuned range-separated hybrid functional with the polarizable continuum model, is applied to a series of eight representative molecular semiconductor crystals. We show that it provides ionization energies, electron affinities, and transport gaps in very good agreement with experimental values as well as with the results of many-body perturbation theory within the GW approximation at a fraction of the computational costs. Hence, this approach represents an easily applicable and computationally efficient tool to estimate the gas-to-crystal-phase shifts of the frontier-orbital quasiparticle energies in organic electronic materials.
Original languageEnglish (US)
Pages (from-to)2906-2916
Number of pages11
JournalJournal of Chemical Theory and Computation
Issue number6
StatePublished - May 26 2016

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