乙醇酸在氩基质中的构象依赖性光解

Photochem Pub Date : 2023-03-31 DOI:10.3390/photochem3020013
J. Ahokas, Timur Nikitin, J. Krupa, Iwona Kosendiak, R. Fausto, M. Wierzejewska, J. Lundell
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引用次数: 0

摘要

采用波长为212、226和230 nm的激光,利用红外光谱研究了乙醇酸三种最稳定的构象(SSC、GAC和AAT)在低温固体氩气基质中的光解和光异构化。本工作拓宽了乙醇酸光化学研究的波长范围,从而扩展了对该化合物整体光化学的认识。提出的乙醇酸光解动力学模型是从最低能构象(SSC)出发的。该模型表明,紫外光仅在SSC和GAC构象之间以及SSC和AAT构象之间诱导异构化。报告了所有反应的相对反应速率系数。这些结果表明,GAC和AAT构象在氩气基质中不会发生直接光解。通过SSC构象的主要光解通道产生甲醛-水络合物。提出的光解机制强调构象的相对丰度可以显著影响分子的光解速率。例如,在GAC和AAT相对浓度较高的情况下,乙醇酸的紫外光解需要GAC和AAT向SSC进行光异构化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Conformational-Dependent Photodissociation of Glycolic Acid in an Argon Matrix
Ultraviolet-induced photodissociation and photo-isomerization of the three most stable conformers (SSC, GAC, and AAT) of glycolic acid are investigated in a low-temperature solid argon matrix using FTIR spectroscopy and employing laser radiation with wavelengths of 212 nm, 226 nm, and 230 nm. The present work broadens the wavelength range of photochemical studies of glycolic acid, thus extending the understanding of the overall photochemistry of the compound. The proposed kinetic model for the photodissociation of glycolic acid proceeds from the lowest energy conformer (SSC). The model suggests that ultraviolet light induces isomerization only between the SSC and GAC conformers and between the SSC and AAT conformers. The relative reaction rate coefficients are reported for all proposed reactions. These results suggest that the direct photodissociation of GAC and AAT conformer does not occur in an argon matrix. The main photodissociation channel via the SSC conformer produces formaldehyde–water complexes. The proposed photodissociation mechanism emphasizes that the conformers’ relative abundancies can significantly affect the photodissociation rate of the molecule. For example, in the case of high relative GAC and AAT concentrations, the ultraviolet photodissociation of glycolic acid requires the proceeding photo-isomerization of GAC and AAT to SSC.
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CiteScore
3.60
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