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|Title:||Optical properties of the atomically precise C₄ core [Au₉(PPh₃)₈]³⁺ cluster probed by transient absorption spectroscopy and time-dependent density functional theory|
|Other Titles:||Optical properties of the atomically precise C(4) core [Au(9)(PPh(3))(8)](3+) cluster probed by transient absorption spectroscopy and time-dependent density functional theory|
|Citation:||The Journal of Physical Chemistry C, 2021; 125(3):2033-2044|
|Publisher:||American Chemical Society|
|Jenica Marie L. Madridejos, Takaaki Harada, Alexander J. Falcinella, Thomas D. Small, Vladimir B. Golovko, Gunther G. Andersson ... et al.|
|Abstract:||Structural isomerism of [Au9(PPh3)8]3+ has been studied experimentally, mostly concerning the symmetry of the Au9 core. Recently, the C4 isomer of [Au9(PPh3)8]3+ has been shown to exist in solution phase while the D2h isomer is present in the solid state [Inorg. Chem.2017, 56, 8319–8325]. In this work, geometric, electronic, and optical properties of C4 [Au9(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 [Au9(PPh3)8]3+ cluster in dichloromethane and methanol solutions are studied using femtosecond transient absorption spectroscopy. [Au9(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 [Au9(PPh3)8]3+, respectively. On the other hand, optical pumping of [Au9(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 ∼0.3 ps. Our combined computational and experimental study reveals that the excitation wavelength-dependent relaxation dynamics of the [Au9(PPh3)8]3+ cluster are related to the different electron densities of the excited states of [Au9(PPh3)8]3+, consistent with it possessing molecular-like electronic states.|
|Rights:||© 2021 American Chemical Society|
|Appears in Collections:||Chemistry and Physics publications|
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