TY - JOUR
T1 - Tracking Photoinduced Au-Au Bond Formation through Transient Terahertz Vibrations Observed by Femtosecond Time-Domain Raman Spectroscopy
AU - Kuramochi, Hikaru
AU - Takeuchi, Satoshi
AU - Iwamura, Munetaka
AU - Nozaki, Koichi
AU - Tahara, Tahei
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/12/11
Y1 - 2019/12/11
N2 - Real-time observation of chemical bond formation and subsequent nuclear rearrangements is an ultimate goal of chemical science. Yet, such attempts have been hampered by the technical difficulty of triggering bond formation at well-defined, desired timing. The trimer of dicyanoaurate complex ([Au(CN)2 -]3) is an ideal system for achieving this aim because the tight covalent Au-Au bonds are formed upon photoexcitation. Despite the apparent simplicity of the system, however, recent time-resolved studies failed to construct a consistent picture of its ultrafast dynamics. Here, we report femtosecond time-domain Raman tracking of ultrafast structural dynamics of the [Au(CN)2 -] trimer upon photoinduced Au-Au bond formation. The obtained Raman data reveal that the Au-Au breathing vibration at â¼90 cm-1 exhibits a gradual frequency upshift in a few picoseconds, demonstrating a continuous bent-to-linear structural change on the triplet-state potential energy surface upon the Au-Au bond formation. The comprehensive ultrafast spectroscopic study settles the controversy on this prototypical molecular assembly.
AB - Real-time observation of chemical bond formation and subsequent nuclear rearrangements is an ultimate goal of chemical science. Yet, such attempts have been hampered by the technical difficulty of triggering bond formation at well-defined, desired timing. The trimer of dicyanoaurate complex ([Au(CN)2 -]3) is an ideal system for achieving this aim because the tight covalent Au-Au bonds are formed upon photoexcitation. Despite the apparent simplicity of the system, however, recent time-resolved studies failed to construct a consistent picture of its ultrafast dynamics. Here, we report femtosecond time-domain Raman tracking of ultrafast structural dynamics of the [Au(CN)2 -] trimer upon photoinduced Au-Au bond formation. The obtained Raman data reveal that the Au-Au breathing vibration at â¼90 cm-1 exhibits a gradual frequency upshift in a few picoseconds, demonstrating a continuous bent-to-linear structural change on the triplet-state potential energy surface upon the Au-Au bond formation. The comprehensive ultrafast spectroscopic study settles the controversy on this prototypical molecular assembly.
UR - http://www.scopus.com/inward/record.url?scp=85076388079&partnerID=8YFLogxK
U2 - 10.1021/jacs.9b06950
DO - 10.1021/jacs.9b06950
M3 - 学術論文
C2 - 31774668
AN - SCOPUS:85076388079
SN - 0002-7863
VL - 141
SP - 19296
EP - 19303
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 49
ER -