title: Real-time observation of tight Au-Au bond formation and relevant coherent motion upon photoexcitation of [Au(CN)2-] oligomers.
abstract: 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 (τ = 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 trimer 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 τ = 2.0 ns, yielding the excited-state tetramer.
authors.affiliation: Graduate School of Science and Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555, Japan. miwamura@sci.u-toyama.ac.jp
authors.forename: Munetaka
authors.initials: M
authors.lastname: Iwamura
authors.forename: Koichi
authors.initials: K
authors.lastname: Nozaki
authors.forename: Satoshi
authors.initials: S
authors.lastname: Takeuchi
authors.forename: Tahei
authors.initials: T
authors.lastname: Tahara