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从C1 1(51P1)<--X10+(51S0)振动跃迁的激发光谱推导得到的CdHe范德华复合物的原子间势参数。

Interatomic potential parameters of CdHe van der Waals complex derived from excitation spectrum of the C1 1(51P1)<--X10+(51S0) vibrational transition.

作者信息

Czajkowski M A, Kedzierski W, Koperski J

机构信息

Department of Physics, University of Windsor, Windsor, Ontario, Canada.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2007 Jul;67(3-4):730-6. doi: 10.1016/j.saa.2006.08.025. Epub 2006 Aug 25.

Abstract

The first time observed excitation spectrum of the C(1)1(5(1)P(1))<--X(1)0+(5(1)S(0)) transition in CdHe van der Waals molecules is reported. Vibrational spectrum in the UV region (2286.0-2296 A) was excited in a continuous molecular-jet-expansion beam of CdHe seeded in helium using an in-house-built nitrogen-dye laser system. The excitation spectrum exhibits two vibrational components (v'<--v''=0) highly broadened by means of unresolved rotational structure and some additional contributions of "hot-bands" components (v'<--v''=1). The last effect is due to an extremely small separation of the vibrational levels in the ground X(1)0+ state of the CdHe molecule, where v'=0 vibrational level is separated from v''=0 by merely 6.0 cm(-1). It follows therefore that even in an extremely cold environment (T(v) approximately 10K) of a jet-expansion beam the population of v''=1 level is feasible, due to some residual collisions, and hence the v'<--v'=1 transitions are highly probable. The assignment of vibrational bands and numerical analysis of the spectrum was based and obtained with the aid of a rigorous computer simulation of the C(1)1<--X(1)0+ transition including the impact of rotational structure and hot-bands contributions. As a result we obtained optical potential parameters of the C(1)1(5(1)P(1)) state of CdHe molecule which are further discussed in terms of our recent (and only existing) experimental results regarding the X(1)0+, B1(5(3)P(1)) and A0+(5(3)P(1)) states of CdHe as well as in terms of ab initio calculations results.

摘要

报道了首次观测到的CdHe范德瓦尔斯分子中C(1)1(5(1)P(1))←X(1)0+(5(1)S(0))跃迁的激发光谱。利用自制的氮染料激光系统,在氦气中注入CdHe的连续分子束膨胀光束中,激发了紫外区域(2286.0 - 2296 Å)的振动光谱。激发光谱显示出两个因未分辨的转动结构而高度展宽的振动成分(v'←v'' = 0)以及“热带”成分(v'←v'' = 1)的一些额外贡献。后一种效应是由于CdHe分子基态X(1)0+中振动能级的间距极小,其中v' = 0振动能级与v'' = 0仅相差6.0 cm(-1)。因此可以推断,即使在喷注膨胀光束的极冷环境(T(v)约为10K)中,由于一些残余碰撞,v'' = 1能级的布居也是可行的,因此v'←v' = 1跃迁很有可能发生。振动带的归属和光谱的数值分析是基于并借助对C(1)1←X(1)0+跃迁的严格计算机模拟得到的,该模拟包括转动结构和热带贡献的影响。结果我们得到了CdHe分子C(1)1(5(1)P(1))态的光学势参数,并根据我们最近(也是唯一现有的)关于CdHe的X(1)0+、B1(5(3)P(1))和A0+(5(3)P(1))态的实验结果以及从头算计算结果对其进行了进一步讨论。

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