Photoisomerization of acetone via Rydberg excitation

IF 1.7 4区化学 Q3 Chemistry Journal of Chemical Sciences Pub Date : 2023-05-27 DOI:10.1007/s12039-023-02155-4

Monoj Samanta, Indrani Bhattacharya, Piyali Chatterjee, Koushik Mondal, Tapas Chakraborty

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Abstract

Acetone photochemistry upon excitation by vacuum ultraviolet (VUV) radiation of photon energy 7.75 eV has been investigated under a cryogenic condition of an argon matrix (8 K) and also by shining the molecule seeded in an effusive beam of argon prior to matrix deposition on a pre-cooled KBr window, where the photo-products get trapped in the argon matrix. Product analysis by infrared spectroscopy reveals appearance of the characteristic enolic O-H stretching fundamental at 3622 cm^-1 and other bands in the infrared fingerprint region, including C=C stretching only in the gas phase. The findings reveal the opening of a new isomerization reaction channel of acetone over the popular Norrish type-I α-CC bond cleavage upon VUV excitation to high-lying Rydberg states.

Graphical abstract:

SYNOPSIS Photochemical transformation of acetone upon excitation by vacuum ultraviolet radiation of photon energy 7.75 eV is reported under a cryogenic condition of an argon matrix (8 K). Infrared spectroscopic analysis of the products reveals that acetone isomerizes to the enolic form, 1-propene-2-ol, upon excitation to the high-lying Rydberg states.

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丙酮在里德伯激发下的光异构化

在低温条件下(8 K)氩气基质下，研究了光子能量为7.75 eV的真空紫外(VUV)辐射激发下的丙酮光化学反应，并在预冷的KBr窗口上沉积基质之前，将种子分子在氩气流光束中照射，使光产物被困在氩气基质中。红外光谱分析表明，在3622 cm-1和红外指纹区其他波段出现了特征烯醛O-H拉伸基谱，包括仅在气相中出现的C=C拉伸。这一发现揭示了丙酮在VUV激发至高Rydberg态时，在常见的Norrish i型α-CC键裂解上开辟了一个新的异构化反应通道。摘要:本文报道了在低温条件下，以光子能量为7.75 eV的真空紫外辐射在氩气基质(8 K)下激发丙酮的光化学反应。产物的红外光谱分析表明，丙酮在激发到高里德堡态后异构化为烯醇形式1-丙烯-2-醇。

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来源期刊

Journal of Chemical Sciences Chemistry-General Chemistry

CiteScore

2.90

自引率

5.90%

发文量

107

审稿时长

12 months

期刊介绍： Journal of Chemical Sciences is a monthly journal published by the Indian Academy of Sciences. It formed part of the original Proceedings of the Indian Academy of Sciences – Part A, started by the Nobel Laureate Prof C V Raman in 1934, that was split in 1978 into three separate journals. It was renamed as Journal of Chemical Sciences in 2004. The journal publishes original research articles and rapid communications, covering all areas of chemical sciences. A significant feature of the journal is its special issues, brought out from time to time, devoted to conference symposia/proceedings in frontier areas of the subject, held not only in India but also in other countries.