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Spontaneous-Symmetry-Breaking Charge Separation Induced by Pseudo-Jahn-Teller Distortion in Organic Photovoltaic
Takeaki Zaima1,2, Wataru Ota1,2, Naoki Haruta1,2
1Fukui Institute for Fundamental Chemistry, Kyoto University, Takano Nishibiraki-cho 34-4, Sakyo-ku, Kyoto 606-8103, Japan.
Abstract:
The driving force of charge separation in the initial photovoltaic conversion process is theoretically investigated using ITIC, a nonfullerene acceptor material for organic photovoltaic devices. The density functional theory calculations show that the pseudo-Jahn-Teller (PJT) distortion of the S1 excimer state induces spontaneous symmetry-breaking charge separation between the identical ITIC molecules even without the asymmetry of the surrounding environment. The strong PJT effect arises from the vibronic coupling between the pseudodegenerate S1 and S2 excited states with different irreducible representations (irreps), i.e., A for S1 and A for S2, via the asymmetric vibrational mode with the A irrep. The vibrational mode responsible for the spontaneous polarization, which is opposite in one ITIC monomer and the other, is the intramolecular C-C stretching vibration between the core IT and terminal IC units. These results suggest that controlling the PJT effect can improve the charge separation efficiency of the initial photovoltaic conversion process.
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