Theoretical Study on Photoinduced Triplet Electron Transfer at the Interface of Pd-Octaethylporphyrin and Tungsten Disulfide  

八乙基卧啉钯与二硫化钨界面处光诱导的三重态电子转移过程的理论研究

作　　者：Yang Zhang Wen-Qi Zhao Wen-Kai Chen Xiao-Ying Xie Wei-Hai Fang Ganglong Cui 张杨;赵文淇;陈文恺;解晓英;方维海;崔刚龙(北京师范大学化学学院,理论与计算光化学教育部重点实验室,北京100875;河北师范大学化学与材料科学学院,石家庄050024;烟台大学化学化工学院,烟台264005)

机构地区：[1]Key Laboratory of Theoretical and Computational Photochemistry,Ministry of Education,College of Chemistry,Beijing Normal University,Beijing 100875,China [2]College of Chemistry and Materials Science,Hebei Normal University,Shijiazhuang 050024,China [3]School of Chemistry and Chemical Engineering,Yantai University,Yantai 264005,China

出　　处：《Chinese Journal of Chemical Physics》2025年第1期113-124,I0050-I0054,I0057,共18页化学物理学报(英文)

基　　金：supported by the Fundamental Re-search Funds for the Central Universities(Ganglong Cui)and National Key Research and Development Pro-gram of China(No.2021YFA1500703 to Ganglong Cui);National Natural Science Foundation of China(No.22103067 to Xiao-Ying Xie)and Natural Science Foundation of Shandong Province(No.ZR2021QB105 to Xiao-Ying Xie).

摘　　要：Heterostructures of organic semi-conductors and transition metal dichalcogenides(TMDs)are viable candidates for superior optoelec-tronic devices.Photoinduced inter-facial charge transfer is crucial for the performance efficiency of such devices,yet the underlying mecha-nism,especially the roles of optical-ly dark triplets and spatially sepa-rated charge transfer states,is poorly understood.In the present work,we obtain the struc-tures of distinct excited states and investigate how they are involved in the charge transfer process at the Pd-octaethylporphyrin(PdOEP)and WS_(2) interface in terms of their energies and couplings.The results show that electron transfer from the triplet PdOEP formed via intersystem crossing prevails over direct electron transfer from the singlet(two orders of magnitude faster).Further analysis reveals that the relatively higher rate of triplet electron transfer compared to singlet electron transfer is mainly attributed to a smaller reorganization energy,which is dominated by the out-of-plane vibrations of the organic component.The work emphasizes the important roles of the optically dark triplets in the electron transfer of the PdOEP@WS_(2) heterostructure,and provides valuable theoretical insights for further improv-ing the optoelectronic performance of TMD-based devices.有机半导体和过渡金属硫族化合物形成的异质结是构建高性能光电器件潜在的理想材料.光诱导的界面间电荷转移过程影响着此类器件的性能.然而,有机半导体和过渡金属硫族化合物之间的电荷转移机制尚不清楚,尤其是三重态和电荷转移态在其中发挥的作用不明确.在本工作中,优化得到了八乙基卟啉钯和二硫化钨异质结不同的激发态结构,并根据它们的能量和电子耦合分析了不同激发态是如何参与界面电子转移过程的.计算结果表明,相较于单重态电子转移,从八乙基卟啉钯到二硫化钨的三重态电子转移速率提高了两个数量级.深入分析显示,八乙基卟啉钯的面外振动使得三重态电子转移过程的重组能较小,最终导致三重态电子转移明显快于单重态电子转移,本工作强调了三重激发态在八乙基卟啉钯和二硫化钨异质结电子转移中的重要作用,为进一步提高过渡金属硫族化合物类器件的光电性能提供了理论指导.

关 键 词：Interfacial charge transfer Photoinduced carrier dynamics Theoretical study Pd-octaethylporphyrin Triplet electron transfer Tungsten disulfide 

分 类 号：O64[理学—物理化学]