Photodissociation and formation of an ion-pair in CH2FCl (HCFC-31)

IF 3.4 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Journal of Computational Chemistry Pub Date : 2023-11-11 DOI:10.1002/jcc.27257

Albert J. F. W. H. de S. Silva, Gessenildo P. Rodrigues, Elizete Ventura, Silmar A. do Monte

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Abstract

Although CH₂FCl (HCFC-31) recently became of great atmospheric importance, studies concerning its excited states are almost nonexistent. Several excited singlet states were studied (valence nσ* and Rydberg n3s, n3p, σ3s, and σ3p) through highly correlated multireference configuration interaction with singles and doubles, including extensivity correction. Comparison with the states of CH₃Cl indicates a strong influence of the F atom. Potential energy curves suggest formation of an electrostatically bound complex that relaxes to a hydrogen-bonded contact ion-pair (HBCIP) which can decay yielding CH₂F + Cl or to the ground state minimum of CH₂FCl. The HBCIP has a dipole moment of 9.57 D, a CI wavefunction described as 0.65ionic + 0.20biradical and it is strongly bonded by 4.72 eV. Its H bond has characteristics of moderate and strong H bonds. The simulated absorption spectrum confirms the nσ* assignment for the first and suggests the n3s + n3p_σ assignment for the second band.

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CH2 FCl（HCFC-31）中离子对的光解和形成。

尽管CH2-FCl（HCFC-31）最近在大气中变得非常重要，但关于其激发态的研究几乎不存在。通过与单重态和双重态高度相关的多参考组态相互作用，包括外延校正，研究了几种激发的单线态（价态nσ*和里德堡n3s、n3p、σ3s和σ3p）。与CH3 Cl的状态的比较表明F原子的强烈影响。势能曲线表明形成了静电结合的络合物，该络合物弛豫为氢键接触离子对（HBCIP），该对可以衰变产生CH2 F + Cl或至CH2-FCl的基态最小值。HBCIP的偶极矩为9.57D，CI波函数描述为0.65离子 + 0.20双自由基，通过4.72牢固结合它的H键具有中等和强H键的特性。模拟的吸收光谱证实了第一次的nσ*分配，并提出了n3s + n3pσ赋值。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Computational Chemistry 化学-化学综合

CiteScore

6.60

自引率

3.30%

发文量

247

审稿时长

1.7 months

期刊介绍： This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.