title: Femtosecond X-ray solution scattering reveals that bond formation mechanism of a gold trimer complex is independent of excitation wavelength.
abstract: The [Au(CN)2 (-)]3 trimer in water experiences a strong van der Waals interaction between the d(10) gold atoms due to large relativistic effect and can serve as an excellent model system to study the bond formation process in real time. The trimer in the ground state (S0) exists as a bent structure without the covalent bond between the gold atoms, and upon the laser excitation, one electron in the antibonding orbital goes to the bonding orbital, thereby inducing the formation of a covalent bond between gold atoms. This process has been studied by various time-resolved techniques, and most of the interpretation on the structure and dynamics converge except that the structure of the first intermediate (S1) has been debated due to different interpretations between femtosecond optical spectroscopy and femtosecond X-ray solution scattering. Recently, the excitation wavelength of 267 nm employed in our previous scattering experiment was suggested as the culprit for misinterpretation. Here, we revisited this issue by performing femtosecond X-ray solution scattering with 310 nm excitation and compared the results with our previous study employing 267 nm excitation. The data show that a linear S1 structure is formed within 500 fs regardless of excitation wavelength and the structural dynamics observed at both excitation wavelengths are identical to each other within experimental errors.
authors.forename: Kyung Hwan
authors.initials: KH
authors.lastname: Kim
authors.forename: Jong Goo
authors.initials: JG
authors.lastname: Kim
authors.forename: Key Young
authors.initials: KY
authors.lastname: Oang
authors.forename: Tae Wu
authors.initials: TW
authors.lastname: Kim
authors.forename: Hosung
authors.initials: H
authors.lastname: Ki
authors.forename: Junbeom
authors.initials: J
authors.lastname: Jo
authors.affiliation: Department of Chemistry, Inha University , Incheon 402-751, South Korea.
authors.forename: Jeongho
authors.initials: J
authors.lastname: Kim
authors.affiliation: Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK) , 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan.
authors.forename: Tokushi
authors.initials: T
authors.lastname: Sato
authors.affiliation: Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK) , 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan.
authors.forename: Shunsuke
authors.initials: S
authors.lastname: Nozawa
authors.affiliation: Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK) , 1-1 Oho, Tsukuba, Ibaraki 305-0801, Japan.
authors.forename: Shin-Ichi
authors.initials: S
authors.lastname: Adachi
authors.forename: Hyotcherl
authors.initials: H
authors.lastname: Ihee