Luo Yuting, Wang Pu, Pei Yong
Department of Chemistry, Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, Xiangtan University, Xiangtan, Hunan 411105, China.
State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming 650093, China.
J Phys Chem Lett. 2025 Apr 17;16(15):3705-3714. doi: 10.1021/acs.jpclett.5c00395. Epub 2025 Apr 4.
Ligand-protected copper nanoclusters (CuNCs) have attracted considerable attention in both fundamental research and practical applications due to their easy availability, environmental friendliness, and exceptional optical properties. In this study, density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were employed to investigate the photoluminescence (PL) mechanism of two-electron (2) cluster [Au@Cu(SCHCH)(P(CHCH))] () and zero-electron (0) cluster [Cl@Cu(SCHCH)(P(CHCH))] () to explore the impact of the central atom on the PL mechanisms of CuNCs. The accuracy of various exchange-correlation (XC) functionals used for fluorescence and phosphorescence energy calculations was evaluated. The BP86 and PBE0 functionals were used to calculate the radiative and nonradiative transition processes of the two clusters. Theoretical calculations showed that enhanced spin-orbit coupling, larger transition dipole moments, more significant orbital overlap, and smaller Huang-Rhys factors and reorganization energies were the main reasons for the higher PL quantum yield (PLQY) of than . These findings provide important insights into the central atom effect of CuNCs and valuable guidance for their design and optimization in optical applications.
配体保护的铜纳米团簇（CuNCs）因其易于制备、环境友好和优异的光学性质，在基础研究和实际应用中都引起了相当大的关注。在本研究中，采用密度泛函理论（DFT）和含时密度泛函理论（TD-DFT）计算来研究双电子（2）团簇[Au@Cu(SCHCH)(P(CHCH))]（）和零电子（0）团簇[Cl@Cu(SCHCH)(P(CHCH))]（）的光致发光（PL）机制，以探讨中心原子对CuNCs的PL机制的影响。评估了用于荧光和磷光能量计算的各种交换相关（XC）泛函的准确性。使用BP86和PBE0泛函来计算两个团簇的辐射和非辐射跃迁过程。理论计算表明，增强的自旋轨道耦合、更大的跃迁偶极矩、更显著的轨道重叠以及更小的黄昆因子和重组能是比具有更高的PL量子产率（PLQY）的主要原因。这些发现为CuNCs的中心原子效应提供了重要见解，并为其在光学应用中的设计和优化提供了有价值的指导。
