通过负离子零动能光电子能谱对ClO、OClO、ClOO和ClAr进行质量选择性气相研究。

Mass selective gas phase study of ClO, OClO, ClOO and ClAr by anion-ZEKE-photoelectron spectroscopy.

作者信息

Distelrath V, Boesl U

机构信息

Institut fur Physikalische und Theoretische Chemie, Technische Universitat Munchen, Garching, Germany.

出版信息

Faraday Discuss. 2000(115):161-74; discussion 175-204. doi: 10.1039/a909618c.

DOI:10.1039/a909618c

PMID:11040508

Abstract

Anion-ZEKE-photoelectron spectra of ClO-, OClO-, ClOO- and the van der Waals cluster ArCl- have been measured. Refined or new values for the electron affinity of ClO, OClO and ClOO have been found. The peak positions in these spectra are in very good agreement with former ClO- and OClO- anion-photoelectron spectra (K. M. Gilles, M. L. Polak and W. C. Lineberger, J. Chem. Phys., 1992, 96, 8012) and a recent ArCl- anion-ZEKE spectrum (T. Lenzer, I. Yourshaw, M. Furlanetto, G. Reiser and D. Neumark, J. Chem. Phys., 1992, 110, 9578). The higher resolution of our anion-ZEKE-photoelectron spectrum of OClO- led to a refined assignment of the corresponding anion-photoelectron spectrum. In addition, a strong difference in the relative intensities of the vibrational peaks has been found in the anion-ZEKE-spectrum of OClO- in comparison with the anion-photoelectron spectrum. For the first time, mass selective spectroscopic information has been obtained for ClOO. The strong similarity to the ArCl- spectrum indicates a weakly bound van der Waals cluster Cl.O2. Binding energies of the anion, neutral ground and neutral excited state could be deduced. These are in good agreement with the electron affinities of Cl and ClOO, but differ from theoretical values (K. A. Peterson and H. J. Werner, J. Chem. Phys., 1992, 96, 8948) by a factor of 4.5 and from thermochemically determined values (J. M. Nicovich, K. D. Kreutter, C. J. Shackelford and P. H. Wine, Chem. Phys. Lett., 1991, 179, 367 and S. Baer, H. Hippler, R. Rahn, M. Siefke, N. Seitzinger and J. Troe, J. Chem. Phys., 1991, 95, 6463) by a factor of 9.

摘要

已测量了ClO⁻、OClO⁻、ClOO⁻的阴离子零动能光电子能谱以及范德华簇ArCl⁻的能谱。已得到ClO、OClO和ClOO电子亲和势的精确值或新值。这些能谱中的峰位置与之前的ClO⁻和OClO⁻阴离子光电子能谱（K.M.吉莱斯、M.L.波拉克和W.C.莱恩伯格，《化学物理杂志》，1992年，96卷，8012页）以及最近的ArCl⁻阴离子零动能能谱（T.伦泽、I.尤尔绍、M.弗拉内托、G.赖泽和D.纽马克，《化学物理杂志》，1992年，110卷，9578页）非常吻合。我们对OClO⁻的阴离子零动能光电子能谱具有更高的分辨率，这使得对相应阴离子光电子能谱的归属更加精确。此外，与阴离子光电子能谱相比，在OClO⁻的阴离子零动能能谱中发现了振动峰相对强度的显著差异。首次获得了ClOO的质量选择光谱信息。与ArCl⁻能谱的高度相似性表明存在弱束缚的范德华簇Cl.O₂。可以推导出阴离子、中性基态和中性激发态的结合能。这些与Cl和ClOO的电子亲和势吻合良好，但与理论值（K.A.彼得森和H.J.维尔纳，《化学物理杂志》，1992年，96卷，8948页）相差4.5倍，与热化学测定值（J.M.尼科维奇、K.D.克鲁特、C.J.沙克尔福德和P.H.瓦恩，《化学物理快报》，1991年，179卷，367页以及S.贝尔、H.希普勒、R.拉恩、M.西夫克、N.塞茨inger和J.特罗，《化学物理杂志》，1991年，95卷，6463页）相差9倍。