Infrared spectra of gaseous peroxychloroformyl radical ClC(O)OO: A key intermediate in the conversion of CO to CO2 in the Venus atmosphere

IF 1.4 4区 物理与天体物理 Q4 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL Journal of Molecular Spectroscopy Pub Date : 2023-03-01 DOI:10.1016/j.jms.2023.111771
Bedabyas Behera , Yuan-Pern Lee
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Abstract

The peroxychloroformyl radical, ClC(O)OO, was proposed to play a critical role in the catalytic conversion of CO to CO2 in the atmosphere of Venus, but direct spectral characterization of this species in the gaseous phase is lacking. Photolysis of a mixture of (ClCO)2 and O2 near 50 Torr with laser light at 248 nm produced absorption bands of CO, CO2, Cl2CO, and transient absorption bands that can be assigned to ClCO, trans-ClC(O)OO, and cis-ClC(O)OO. Bands at 937, 1014, and 1902 cm−1 are assigned to the OCO bending (ν3), overtone of C−Cl stretching (2ν5), and C=O stretching (ν1) modes of trans-ClC(O)OO. According to rotational contour simulations with PGOPHER, two bands ∼ 1883 and ∼ 1928 cm−1 also contribute to the band near 1902 cm−1; they might be assigned to the ν2 + ν8 + ν9 mode of cis-ClC(O)OO and the ν2 + ν4 mode of trans-ClC(O)OO, whereas the band near 937 cm−1 might have contribution from the 2ν6 (overtone of OC=O bending) mode of cis-ClC(O)OO near 928 cm−1. Bands at 964, 1110, and 1837 cm−1 are assigned to the anti-phase C–O and O–O stretching (ν3), O–O stretching (ν2), and C=O stretching (ν1) modes of cis-ClC(O)OO. The band near 1837 cm−1 might have contribution from the 2ν3 mode of trans-ClC(O)OO and cis-ClC(O)OO near 1829 and < 1829 cm−1, respectively. From the temporal evolution of CO and CO2, we confirmed that the addition of O2 to the photolyzed (ClCO)2 system to form ClC(O)OO enhanced the formation of CO2, supporting the proposed catalytic mechanism.

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气态过氧化氯甲酰基自由基ClC(O)OO的红外光谱:金星大气中CO转化为CO2的关键中间体
过氧氯甲酰基自由基ClC(O)OO被认为在金星大气中CO转化为CO2的催化过程中起关键作用,但缺乏对该物种气相的直接光谱表征。(ClCO)2和O2的混合物在50torr附近用激光在248 nm处光解产生CO、CO2、Cl2CO的吸收带,以及ClCO、trans-ClC(O)OO和顺式clc (O)OO的瞬态吸收带。937,1014和1902 cm−1波段被分配给反式clc (O)OO的OCO弯曲(ν3), C−Cl拉伸的泛音(2ν5)和C=O拉伸(ν1)模式。根据PGOPHER的旋转等高线模拟,两个波段~ 1883和~ 1928 cm−1也贡献了1902 cm−1附近的波段;它们可能属于顺式clc (O)OO的ν2 + ν8 + ν9模式和反式clc (O)OO的ν2 + ν4模式,而937 cm−1附近的波段可能来自928 cm−1附近的顺式clc (O)OO的2ν6 (OC=O弯曲的泛音)模式。964、1110和1837 cm−1处的波段被分配给顺式clc (O)OO的反相C - O和O - O拉伸(ν3)、O - O拉伸(ν2)和C=O拉伸(ν1)模式。1837 cm−1附近的波段可能来自1829和<附近的反式clc (O)OO和顺式clc (O)OO的2ν3模式;分别为1829 cm−1。从CO和CO2的时间演化中,我们证实了O2加入到光解(ClCO)2体系中形成ClC(O)OO促进了CO2的形成,支持了所提出的催化机制。
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来源期刊
CiteScore
2.70
自引率
21.40%
发文量
94
审稿时长
29 days
期刊介绍: The Journal of Molecular Spectroscopy presents experimental and theoretical articles on all subjects relevant to molecular spectroscopy and its modern applications. An international medium for the publication of some of the most significant research in the field, the Journal of Molecular Spectroscopy is an invaluable resource for astrophysicists, chemists, physicists, engineers, and others involved in molecular spectroscopy research and practice.
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