Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford, OX1 3QZ, UK.
Phys Chem Chem Phys. 2014 Jan 14;16(2):458-66. doi: 10.1039/c3cp53214c.
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.
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。