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[交流] 分享激光分解稀土茂和物，以及激发态分子动力学模拟的文章

最近我们组在 Organometallics 杂志发表了题为Photofragmentation of Gas-Phase Lanthanide Cyclopentadienyl Complexes: Experimental and Time-Dependent Excited-State Molecular Dynamics的文章，文章阐述了用时间飞行质谱检测激光分解的气态稀土配合物(分子束)碎片, 研究气态配合物的光分解机理，并且使用激发态分子动力学模拟来理论预测和证实光分解机理。文章涉及时间飞行质谱搭建及检测，气态配合物分子束的形成，质谱的分析，激发态分子动力学模拟，以及如何用把理论模型应用到实验中等，文章13页，引文49篇。希望得到大家批评指正，共同学习。

摘要：
Unimolecular gas-phase laser-photodissociation reaction mechanisms of open-shell lanthanide cyclopentadienyl
complexes, Ln(Cp)3 and Ln(TMCp)3, are analyzed from experimental and computational perspectives. The most probable
pathways for the photoreactions are inferred from photoionization time-of-flight mass spectrometry (PI-TOF-MS), which
provides the sequence of reaction intermediates and the distribution of final products. Time-dependent excited-state molecular
dynamics (TDESMD) calculations provide insight into the electronic mechanisms for the individual steps of the laser-driven
photoreactions for Ln(Cp)3. Computational analysis correctly predicts several key reaction products as well as the observed
branching between two reaction pathways: (1) ligand ejection and (2) ligand cracking. Simulations support our previous
assertion that both reaction pathways are initiated via a ligand-to-metal charge-transfer (LMCT) process. For the more complex
chemistry of the tetramethylcyclopentadienyl complexes Ln(TMCp)3, TMESMD is less tractable, but computational geometry
optimization reveals the structures of intermediates deduced from PI-TOF-MS, including several classic “tuck-in” structures and
products of Cp ring expansion. The results have important implications for metal−organic catalysis and laser-assisted metal−
organic chemical vapor deposition (LCVD) of insulators with high dielectric constants.

Photofragmentation of Gas-Phase Lanthanide Cyclopentadienyl Complexes: Experimental and Time-Dependent Excited-State Molecular Dynamics
J Chen, AM Hochstatter, D Kilin, PS May, Q Meng… Organometallics 2014, 33, 1574−1586

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