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非极性一氧化二氮二聚体:混合 14N2O-15N2O 二聚体的基础以及涉及 Bu、分子间弯曲的 (14N2O)2 和 (15N2O)2 的新组合带。

Nonpolar nitrous oxide dimer: fundamentals of the mixed 14N2O-15N2O dimer and new combination bands of (14N2O)2 and (15N2O)2 involving the Bu, intermolecular bend.

机构信息

Department of Physics and Astronomy, University of Calgary, Calgary, Alberta, Canada.

出版信息

Phys Chem Chem Phys. 2009 Sep 21;11(35):7585-8. doi: 10.1039/b905373e.

Abstract

Spectra of the nonpolar nitrous oxide dimer in the region of the N2O v1 fundamental band are observed in a pulsed supersonic slit jet expansion probed with a tunable diode laser. Four bands are analysed: two fundamentals of the mixed 14N2O-15N2O dimer and combination bands involving the intermolecular disrotation of the monomers (Bu intermolecular bend) for both (14N2O)2 and (15N2O)2. Because the determination of this intermolecular frequency relies on the experimentally unknown frequency of the (forbidden) symmetric fundamental, we used previously published ab initio results and their proximity to our experimental values to assign the upper state of the combination bands. The resulting intermolecular disrotation frequencies are 42.3(1.0) and 41.6(1.0) cm(-1) for the (14N2O)2 and (15N2O)2, respectively. This represents the first observation of the mixed 14N2O-15N2O dimer, and the direct determination of a second intermolecular frequency for the nonpolar (N2O)2.

摘要

在脉冲超音速狭缝射流膨胀中,用可调谐二极管激光探测到 N2O v1 基频带区域中非极性一氧化二氮二聚体的光谱。分析了四个带:两个混合的 14N2O-15N2O 二聚体的基频和涉及单体(Bu 内分子弯曲)内分子旋转的组合带,对于(14N2O)2 和(15N2O)2 都是如此。因为这个内分子频率的确定依赖于实验上未知的(禁止)对称基频,所以我们使用了以前发表的从头算结果及其与我们实验值的接近程度来分配组合带的上态。得到的内分子旋转频率分别为 42.3(1.0)和 41.6(1.0)cm-1,对于(14N2O)2 和(15N2O)2 分别如此。这代表了混合的 14N2O-15N2O 二聚体的首次观察,以及非极性(N2O)2 的第二个内分子频率的直接确定。

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