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对臭氧的对称同位素分子16O3和18O3在10400cm-1附近预解离的振转电子结构的分析贡献:[3A2(3(2)(0)) ← X1A1(0(0)(0))]和3B2 ← X1A1 。

Contribution to the analysis of the predissociated rovibronic structure of the symmetric isotopomers 16O3 and 18O3 of ozone near 10,400 cm-1): [3A2(3(2)(0)) <-- X1A1(0(0)(0))] and 3B2 <-- X1A1.

作者信息

Wannous G, Bouvier A J, El Helou Z, Chillier X, Churassy S, Bacis R, Campargue A, Weirauch G, Judge R H

机构信息

Laboratoire de Spectrométrie Ionique et Moléculaire, UMR CNRS No. 5579, Université Claude Bernard Lyon 1, 43 Boulevard du 11 Novembre 1918, 69622 Villeurbanne Cedex, France.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2004 Mar;60(4):889-98. doi: 10.1016/S1386-1425(03)00316-0.

DOI:10.1016/S1386-1425(03)00316-0
PMID:15036100
Abstract

The absorption spectrum of ozone was recorded at low temperatures (down to -135 degrees C) by high resolution Fourier transform spectrometry and intra cavity laser absorption spectroscopy (ICLAS) near 10,400 cm-1. A preliminary analysis of the rotational structure of the absorption spectra of 16O3 and 18O3 shows that this spectral region corresponds to a superposition of two different electronic transitions, one with a very broad rotational structure, showing for the first time the asymmetric stretching frequency mode nu3 of the electronic state 3A2, the other formed by a completely diffuse band, probably the 2(1)(0) band of a new transition due to the triplet electronic state 3B2. Predissociation effects induce large broadening of the rotational lines for the transition centered at 10,473 cm-1 identified as the 3(2)(0) band of the 3A2 <-- X1A1 electronic transition. The rotational structure cannot be analyzed directly but instead the band contour method was used to confirm the symmetry of the transition and to estimate the spectroscopic constants for the 16O isotopomer. The origin of the band is at 10,473 +/- 3 cm-1 and the value of the 16O3(3A2) antisymmetric stretching frequency mode is equal to 460 +/- 2 cm-1. We believe that the diffuse band is due to the 3B2 state and is located at about 10,363 +/- 3 cm-1 for 16O3 and 10,354 +/- 3 cm-1 for 18O3. The isotopic rules confirm the different results obtained for 18O3 and 16O3.

摘要

通过高分辨率傅里叶变换光谱法和腔内激光吸收光谱法(ICLAS),在10400厘米-1附近的低温(低至-135摄氏度)下记录了臭氧的吸收光谱。对16O3和18O3吸收光谱的转动结构进行的初步分析表明,该光谱区域对应于两种不同电子跃迁的叠加,一种具有非常宽的转动结构,首次展示了电子态3A2的不对称伸缩频率模式ν3,另一种由完全弥散的带形成,可能是由于三重态电子态3B2导致的新跃迁的2(1)(0)带。预解离效应导致以10473厘米-1为中心的跃迁的转动谱线大幅展宽,该跃迁被确定为3A2<--X1A1电子跃迁的3(2)(0)带。转动结构无法直接分析,而是采用带轮廓法来确认跃迁的对称性,并估算16O同位素分子的光谱常数。该带的起源位于10473±3厘米-1,16O3(3A2)的反对称伸缩频率模式值等于460±2厘米-1。我们认为,弥散带归因于3B2态,对于16O3位于约10363±3厘米-1,对于18O3位于约10354±3厘米-1。同位素规则证实了18O3和16O3得到的不同结果。

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