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稀有气体基质中(HCOOH)₂和(DCOOH)₂的红外光谱:与气相光谱的对比研究

Infrared spectra of (HCOOH)(2) and (DCOOH)(2) in rare gas matrices: a comparative study with gas phase spectra.

作者信息

Ito Fumiyuki

机构信息

National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba-West, Tsukuba Ibaraki, Japan.

出版信息

J Chem Phys. 2008 Mar 21;128(11):114310. doi: 10.1063/1.2841078.

Abstract

Infrared absorption spectra of (HCOOH)(2) and (DCOOH)(2) in solid argon, krypton, and xenon matrices have been measured and each fundamental band has been assigned. Spectra in Ar and Kr matrices showed notable splitting in contrast to those in Xe, which suggests a difference in structure of the trapping sites. A comparison with the reported jet-cooled spectra has shown that vibrational structures of the spectra of (HCOOH)(2) and (DCOOH)(2) in the O-H stretching region are preserved in the matrices. On the other hand, the C-O stretching band of (HCOOH)(2) shows a drastic change upon matrix isolation, wherein the Fermi-triad feature observed in gas phase [F. Ito, Chem. Phys. Lett. 447, 202 (2007)] could not be identified. No substantial change of the vibrational structure has been found for matrix-isolated (DCOOH)(2). The differences of the vibrational structures in the matrix-isolation spectra and in the jet-cooled spectra have been qualitatively accounted for using the idea of anharmonic couplings among "matrix-shifted harmonic states."

摘要

已测量了在固态氩、氪和氙基质中(HCOOH)₂和(DCOOH)₂的红外吸收光谱,并对每个基频带进行了归属。与氙基质中的光谱相比,氩和氪基质中的光谱显示出明显的分裂,这表明捕获位点的结构存在差异。与已报道的喷射冷却光谱的比较表明,(HCOOH)₂和(DCOOH)₂在O-H伸缩区域的光谱振动结构在基质中得以保留。另一方面,(HCOOH)₂的C-O伸缩带在基质隔离后发生了剧烈变化,其中在气相中观察到的费米三重态特征[F. Ito,《化学物理快报》447, 202 (2007)]无法识别。对于基质隔离的(DCOOH)₂,未发现振动结构有实质性变化。利用“基质位移谐波态”之间的非谐耦合概念,对基质隔离光谱和喷射冷却光谱中振动结构的差异进行了定性解释。

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