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La(苯)(n = 1和2)的低能光电子成像光谱学

Low-Energy Photoelectron Imaging Spectroscopy of La(benzene) (n = 1 and 2).

作者信息

Silva W Ruchira, Cao Wenjin, Yang Dong-Sheng

机构信息

Department of Chemistry, University of Kentucky , Lexington, Kentucky 40506-0055, United States.

出版信息

J Phys Chem A. 2017 Nov 9;121(44):8440-8447. doi: 10.1021/acs.jpca.7b09750. Epub 2017 Oct 30.

Abstract

La(benzene) (n = 1 and 2) are formed in a pulsed laser-ablation molecular beam source and characterized by low-energy photoelectron imaging spectroscopy. The photoelectron spectrum of La(benzene) displays a strong origin band, a short metal-ligand stretching progression, and a weak ring deformation band. Four isomers are considered for La(benzene), and the preferred structure is an inverse sandwich with two La atoms residing on the opposite sides of the benzene ring. The ground electronic state of the inverse sandwich is A (D) with (5d + π*)6s electron configuration. Ionization removes a La-based 6s electron and yields a A ion. The spectrum of La(benzene) is similar to the zero-electron kinetic energy spectrum reported previously by our group, although the spectral line width is somewhat broader. The measurement of the photoelectron angular distribution of La(benzene) confirms that the ejected electron has largely a p wave character. The metal-ligand bonding of La(benzene) is considerably stronger than that of La(benzene) due to the threefold binding of each La atom in the dilanthanum species and the twofold binding in the monolanthanum complex.

摘要

二镧(苯)(n = 1和2)在脉冲激光烧蚀分子束源中形成,并通过低能光电子成像光谱进行表征。二镧(苯)的光电子能谱显示出一个强的起始带、一个短的金属-配体伸缩跃迁以及一个弱的环变形带。考虑了二镧(苯)的四种异构体,其优选结构是一种反夹心结构,两个镧原子位于苯环的相对两侧。反夹心结构的基态电子态为A(D),具有(5d + π*)6s电子构型。电离去除一个基于镧的6s电子并产生一个A离子。二镧(苯)的光谱与我们小组之前报道的零电子动能光谱相似,尽管谱线宽度稍宽一些。对二镧(苯)的光电子角分布的测量证实,出射电子在很大程度上具有p波特征。由于在二镧物种中每个镧原子的三重键合以及在单镧配合物中的二重键合,二镧(苯)的金属-配体键合比一镧(苯)的要强得多。

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