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成像中性金属团簇的光解离动力学:铜二聚体,Cu2,和氧化铜,CuO。

Imaging the photodissociation dynamics of neutral metal clusters: copper dimer, Cu2, and copper oxide, CuO.

机构信息

Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford, OX1 3QZ, UK.

出版信息

Phys Chem Chem Phys. 2014 Jan 14;16(2):458-66. doi: 10.1039/c3cp53214c.

Abstract

The spectroscopy and UV photodissociation dynamics of Cu2 and CuO have been studied using a combination of one- and two-colour excitation and velocity map imaging. Resonant excitation of Cu2 via the J ← X (1)Σg(+) transition leads to significant fragmentation which is interpreted in terms of a combination of direct dissociation of Cu2(+ 2)Π produced in the resonant two-photon ionization process and dissociation of excited Cu2 states above the ionization threshold. By fitting of the kinetic energy release spectra obtained from the velocity map images, we determine a value for the dissociation energy of the cation of D0 (Cu2(+), X (2)Σg(+)) of 1.713 ± 0.025 eV, which, when combined with known ionization energies, yields D0 (Cu2, X (1)Σg(+)) = 1.886 ± 0.026 eV. In other experiments, resonant two colour (1 + 1') excitation of CuO via a range of excited states (C, D, F, H), yields unusually simple VMI images indicating fragmentation into a single dissociation channel which has been identified as Cu* (2)D3/2 + O* (1)D. Taken together, this data gives a CuO bond dissociation energy of 3.041 ± 0.030 eV. Finally, the production of Cu2(+) with kinetic energy = 705 ± 75 cm(-1) is tentatively interpreted as photolysis of Cu3 yielding Cu* + Cu2 X (1)Σg(+) from which a dissociation energy of Cu3 of 0.605 ± 0.030 eV is deduced.

摘要

使用双色和单光激发结合的方法研究了 Cu2 和 CuO 的光谱和紫外光解动力学。通过共振激发 Cu2 的 J←X(1)Σg+(+)跃迁导致了显著的碎裂,这可以用在共振双光子电离过程中产生的 Cu2+(+2)Π的直接解离以及高于电离阈的激发态 Cu2 的解离来解释。通过对速度映射图像得到的动能释放谱进行拟合,我们确定了阳离子 D0(Cu2(X2Σg+))的离解能 D0 的值为 1.713 ± 0.025 eV,当与已知的电离能结合时,得到 D0(Cu2,X(1)Σg+) = 1.886 ± 0.026 eV。在其他实验中,通过一系列激发态(C、D、F、H)对 CuO 进行共振双色(1+1')激发,得到了非常简单的 VMI 图像,表明碎裂成单一的解离通道,该通道已被鉴定为 Cu*(2)D3/2+O*(1)D。总的来说,这些数据给出了 CuO 的键离解能为 3.041 ± 0.030 eV。最后,具有动能=705 ± 75 cm(-1)的 Cu2(+)的产生被初步解释为 Cu3 的光解,从其中推断出 Cu3 的离解能为 0.605 ± 0.030 eV。

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