Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 2, Pages 538-541Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja310004z
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Funding
- KAKENHI [23750060]
- [22550057]
- [22245005]
- Grants-in-Aid for Scientific Research [22550057, 23750060, 22245005] Funding Source: KAKEN
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Structural dynamics involving tight Au-Au bond formation of excited-state oligomers [Au(CN)(2)(-)](n) was studied using picosecond/femtosecond time-resolved emission and absorption spectroscopy. With selective excitation of the trimer ([Au(CN)(2)(-)](3)) in aqueous solutions, transient absorption due to the excited-state trimer was observed around 600 nm. This transient exhibited a significant intensity increase (tau = 2.1 ps) with a blue shift in the early picosecond time region. Density functional theory (DFT) and time-dependent DFT calculations revealed that the observed spectral changes can be ascribed to a structural change from a bent to a linear staggered structure in the triplet excited-state trimer. The transient absorption also exhibited a clear modulation of the peak position, reflecting coherent nuclear wave packet motion induced by photoexcitation. The frequencies of the coherent motions are 66 and 87 cm(-1), in very good accord with the frequencies of two Au-Au stretch vibrations in the excited state of the trirner calculated by DFT. Time-resolved emission spectra in the subnanosecond time region showed that association of the excited-state trimer with the ground-state monomer proceeds with tau = 2.0 ns, yielding the excited-state tetramer.
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