A combination of time-resolved vibrational spectroscopy and density functional theory techniques have been applied to study the vibrational energy relaxation dynamics of the Re(4,4′-dicyano-2,2′-bipyridine)(CO)₃Cl (Re(CO)₃Cl) catalyst for CO₂ to CO conversion bound to gold surfaces. The kinetics of vibrational relaxation exhibits a biexponential decay including an ultrafast initial relaxation and complete recovery of the ground vibrational state. Ab initio molecular dynamics simulations and time-dependent perturbation theory reveal the former to be due to vibrational population exchange between CO stretching modes and the latter to be a combination of intramolecular vibrational relaxation (IVR) and electron–hole pair (EHP)-induced energy transfer into the gold substrate. EHP-induced energy transfer from the Re(CO)₃Cl adsorbate into the gold surface occurs on the same time scale as IVR of Re(CO)₃Cl in aprotic solvents. Therefore, it is expected to be particularly relevant to understanding the reduced catalytic activity of the homogeneous catalyst when anchored to a metal surface.

中文翻译：

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电子-空穴对诱导的金表面R催化剂的振动能弛豫

结合时间分辨振动光谱学和密度泛函理论技术研究了Re（4,4'-dicyano-2,2'-bipyridine）（CO）₃ Cl（Re（CO ）₃ Cl）用于CO _2的催化剂到CO的转换必须结合到金表面。振动弛豫的动力学表现出双指数衰减，包括超快的初始弛豫和基态振动状态的完全恢复。从头算分子动力学模拟和时变扰动理论揭示，前者是由于CO拉伸模式之间的振动种群交换而后者是分子内振动弛豫（IVR）和电子-空穴对（EHP）诱导的能量的组合转移到金基质中。EHP诱导的从Re（CO）₃ Cl吸附物到金表面的能量转移发生在与Re（CO）_3的IVR相同的时间尺度上非质子传递溶剂中的Cl。因此，预期与锚固在金属表面上时均相催化剂的降低的催化活性特别相关。