Communication: Probing non-equilibrium vibrational relaxation pathways of highly excited C≡N stretching modes following ultrafast back-electron transfer
作者： Michael S. Lynch , Karla M. Slenkamp , Munira Khalil
DOI: 10.1063/1.4731882
关键词: Molecular vibration 、 Oscillation 、 Electron transfer 、 Excited state 、 Spectroscopy 、 Intramolecular force 、 Molecular physics 、 Analytical chemistry 、 Chemistry 、 Hot band 、 Vibrational energy relaxation
摘要: Fifth-order nonlinear visible-infrared spectroscopy is used to probe coherent and incoherent vibrational energy relaxation dynamics of highly excited modes indirectly populated via ultrafast photoinduced back-electron transfer in a trinuclear cyano-bridged mixed-valence complex. The flow excess deposited into four C≡N stretching (νCN) the molecule monitored by performing an IR pump-probe experiment as function photochemical reaction (τvis). Our results provide experimental evidence that nuclear motions are both coherently incoherently coupled electronic charge process. We observe intramolecular among νCN change significantly en route equilibrium. also measures 7 cm−1 shift frequency ∼57 cm−1 oscillation reflecting modulation coupling between probed high-frequency for τvis < 500 fs.
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