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氨-稀有气体体系的分子束研究:各向同性相互作用的特征及对分子间势能本质的深入了解。

Molecular-beam study of the ammonia-noble gas systems: characterization of the isotropic interaction and insights into the nature of the intermolecular potential.

机构信息

Dipartimento di Chimica, Università di Perugia, 06123 Perugia, Italy.

出版信息

J Chem Phys. 2011 Nov 21;135(19):194301. doi: 10.1063/1.3660199.

Abstract

We report new high resolution molecular beam experiments aimed at characterizing the intermolecular interaction in the NH(3)-Ng (Ng = He, Ne, Ar, Kr, Xe) weakly bound complexes. Integral cross section data are obtained over a sufficiently wide velocity range and with rotationally hot NH(3) molecules to produce (except for the NH(3)-He case) a well resolved "glory" quantum interference pattern. Data analysis, carried out by employing a recently proposed potential model, allows unique information on the absolute scale of the intermolecular interaction to be obtained both at long range and at the equilibrium distance. An extensive and internally consistent comparison with the behavior of the corresponding Kr-Ng systems is exploited in order to identify those cases where an interaction component due to charge transfer effects provides an appreciable intermolecular bond stabilization that is clearly distinct from and must be added to the standard van der Waals plus induction picture. The results of the present investigation extend the phenomenology of perturbative charge transfer effects in gas phase complexes involving hydrogenated molecules.

摘要

我们报告了新的高分辨率分子束实验,旨在表征 NH(3)-Ng(Ng = He、Ne、Ar、Kr、Xe)弱束缚复合物中的分子间相互作用。在足够宽的速度范围内并使用旋转加热的 NH(3)分子获得积分截面数据,除了 NH(3)-He 情况外,还产生了一个分辨率良好的“荣耀”量子干涉图案。数据分析通过采用最近提出的势能模型进行,允许在长程和平衡距离上获得关于分子间相互作用绝对尺度的独特信息。我们充分利用与相应 Kr-Ng 系统的行为进行的内部一致比较,以确定在哪些情况下,由于电荷转移效应引起的相互作用分量提供了可观的分子间键稳定化,这显然与标准的范德华加诱导图像不同,并且必须将其添加到该图像中。本研究的结果扩展了涉及氢化分子的气相复合物中微扰电荷转移效应的现象学。

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