Photoelectron Spectroscopic and Theoretical Studies of MmC6F5 Anionic Complexes (M = Pb and Bi; m = 1−4)

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• 作者：Zhang Sun ; Shutao Sun ; Hongtao Liu ; Qihe Zhu ; Zhen Gao ; Zichao Tang
• 刊名：Journal of Physical Chemistry A
• 出版年：2009
• 出版时间：July 16, 2009
• 年：2009
• 卷：113
• 期：28
• 页码：8045-8054
• 全文大小：365K
• 年卷期：v.113,no.28(July 16, 2009)
• ISSN：1520-5215

文摘

The reactions between metal (Pb or Bi) clusters formed by laser ablation and hexafluorobenzene (C₆F₆) seeded in argon carrier gas were studied by a reflectron time-of-flight mass spectrometer combined with a photoelectron spectrometer. The adiabatic electron affinities of the dominant anionic products, Pb_mC₆F₅⁻ and Bi_mC₆F₅⁻ (m = 1−4) complexes, were obtained from the photoelectron spectra with 193 nm photons. It was found that the EAs of Pb_mC₆F₅ are higher than those of the pure Pb_m clusters and that the photoelectron spectra of Bi_mC₆F₅⁻ show some similarities to those of Bi_m+1⁻. Theoretical calculations were carried out to elucidate their geometric structures and bonding modes. The adiabatic detachment energy and simulated spectrum based on Koopmans’ theorem for the optimized structures of each complex were in agreement with the photoelectron spectroscopy results. The most likely structures for each species were obtained. The analysis of the molecular orbital composition provides evidence that the C₆F₅ group contributes a single electron to bind with metal clusters through the M−C σ bond.