期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 125, 期 3, 页码 2033-2044出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.0c08838
关键词
-
资金
- Australian Research Council [LE0989747]
- Adelaide Scholarship International (ASI)
- Future Fuels Cooperative Research Center (FFCRC)
- Australian Research Council [LE0989747] Funding Source: Australian Research Council
The structural isomerism of [Au-9(PPh3)(8)](3+) has been experimentally studied, with the C-4 isomer existing in solution phase and the D-2h isomer present in the solid state. Computational and experimental studies have revealed that the relaxation dynamics of the [Au-9(PPh3)(8)](3+) cluster are wavelength-dependent and related to the electron densities of the excited states.
Structural isomerism of [Au-9(PPh3)(8)](3+) has been studied experimentally, mostly concerning the symmetry of the Au-9 core. Recently, the C-4 isomer of [Au-9(PPh3)(8)](3+) has been shown to exist in solution phase while the D-2h isomer is present in the solid state [Inorg. Chem. 2017, 56, 8319-8325]. In this work, geometric, electronic, and optical properties of C-4 [Au-9(PPh3)(8)](3+) are investigated by using the combined second-order density-functional tight-binding (DFTB2) method and time-dependent density functional theory (TD-DFT) calculations with spin-orbit coupling. Additionally, the excited-state relaxation dynamics of the [Au-9(PPh3)(8)](3+) cluster in dichloromethane and methanol solutions are studied using femtosecond transient absorption spectroscopy. [Au-9(PPh3)(8)](3+) is optically pumped to different excited states by using 432, 532, and 603 nm light. For all three pump wavelengths, the photoexcitation event induces an excited-state absorption (ESA) band centered at 600 nm with decay time constants of 2.0 and 45 ps, which are attributed to intersystem crossing and nonradiative relaxation of [Au-9(PPh3)(8)](3+), respectively. On the other hand, optical pumping of [Au-9(PPh3)(8)](3+) using 432 nm light gives rise to an additional ESA band at 900 nm. This band exhibits fast relaxation through internal conversion with a time constant of similar to 0.3 ps. Our combined computational and experimental study reveals that the excitation wavelength-dependent relaxation dynamics of the [Au-9(PPh3)(8)](3+)cluster are related to the different electron densities of the excited states of [Au-9(PPh3)(8)](3+), consistent with it possessing molecular-like electronic states.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据