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Acta Phys. -Chim. Sin.  2017, Vol. 33 Issue (6): 1171-1180    DOI: 10.3866/PKU.WHXB201704071
Density Functional Theory Studies on Ionization Energies, Electron Affinities, and Polarization Energies of Organic Semiconductors
GUO Zi-Han, HU Zhu-Bin, SUN Zhen-Rong, SUN Hai-Tao
State Key Laboratory of Precision Spectroscopy, and School of Physics and Materials Science, East China Normal University, Shanghai 200062, P. R. China
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Accurate prediction of the energy levels (i.e. ionization potential and electronic affinity) of organic semiconductors is essential for understanding related mechanisms and for designing novel organic semiconductor materials. From a theoretical point of view, a major challenge arises from the lack of a reliable method that can provide not only qualitative but also quantitative predictions at an acceptable computational cost. In this study, we demonstrate an approach, combining the polarizable continuum model (PCM) and the optimally tuned range-separated (RS) functional method, which provides the ionization potentials (IPs), electron affinities (EAs), and polarization energies of a series of molecular semiconductors in good agreement with available experimental values. Importantly, this tuning method can enforce the negative frontier molecular orbital energies (-εHOMO, -εLUMO) that are very close to the corresponding IPs and EAs. The success of this tuning method can be further attributed to the fact that the tuned RS functional can provide a good balance for the description of electronic localization and delocalization effects according to various molecular systems or the same molecule in different phases (i.e. gas and solid). In comparison, other conventional functionals cannot give reliable predictions because the functionals themselves include too low (i.e. PBE) or too high (i.e. M06HF and non-tuned RS functionals) HF%. Therefore, we believe that this PCM-tuned approach represents an easily applicable and computationally efficient theoretical tool to study the energy levels of more complex organic electronic materials.

Key wordsOrganic semiconductor      Density functional theory      Optimally-tuned      Range-separated (RS) functional      Energy level     
Received: 27 December 2016      Published: 07 April 2017
MSC2000:  O641  

The project was supported by the National Natural Science Foundation of China (21603074, 11474096) and Shanghai-International Scientific Cooperation Fund, China (16520721200).

Corresponding Authors: SUN Hai-Tao     E-mail:
Cite this article:

GUO Zi-Han, HU Zhu-Bin, SUN Zhen-Rong, SUN Hai-Tao. Density Functional Theory Studies on Ionization Energies, Electron Affinities, and Polarization Energies of Organic Semiconductors. Acta Phys. -Chim. Sin., 2017, 33(6): 1171-1180.

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