Charge transfer rates in organic semiconductors beyond first-order perturbation: From weak to strong coupling regimes

被引:87
作者
Nan, Guangjun [1 ]
Wang, Linjun [1 ]
Yang, Xiaodi [1 ]
Shuai, Zhigang [1 ,4 ]
Zhao, Yi [2 ,3 ]
机构
[1] Chinese Acad Sci, Inst Chem, BNLMS, Key Lab Organ Solids, Beijing 100190, Peoples R China
[2] Xiamen Univ, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China
[3] Xiamen Univ, Dept Chem, Xiamen 361005, Peoples R China
[4] Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China
关键词
charge exchange; hole mobility; organic semiconductors; NONADIABATIC UNIMOLECULAR REACTIONS; DENSITY-FUNCTIONAL THEORY; FIELD-EFFECT TRANSISTORS; TRANSITION-STATE THEORY; THERMAL RATE CONSTANTS; ELECTRON-TRANSFER; CARRIER MOBILITY; BAND-STRUCTURE; MONTE-CARLO; TRANSPORT;
D O I
10.1063/1.3055519
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Semiclassical Marcus electron transfer theory is often employed to investigate the charge transport properties of organic semiconductors. However, quite often the electronic couplings vary several orders of magnitude in organic crystals, which goes beyond the application scope of semiclassical Marcus theory with the first-order perturbative nature. In this work, we employ a generalized nonadiabatic transition state theory (GNTST) [Zhao , J. Phys. Chem. A 110, 8204 (2004)], which can evaluate the charge transfer rates from weak to strong couplings, to study charge transport properties in prototypical organic semiconductors: quaterthiophene and sexithiophene single crystals. By comparing with GNTST results, we find that the semiclassical Marcus theory is valid for the case of the coupling < 10 meV for quaterthiophene and < 5 meV for sexithiophene. It is shown that the present approach can be applied to design organic semiconductors with general electronic coupling terms. Taking oligothiophenes as examples, we find that our GNTST-calculated hole mobility is about three times as large as that from the semiclassical Marcus theory. The difference arises from the quantum nuclear tunneling and the nonperturbative effects.
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页数:8
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