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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >The Vinyl Radical and Fluorinated Vinyl Radicals, C_2H_(3-n)F_n (n = 0-3), and Corresponding Anions: Comparison with the Isoelectronic Complexes [X···YCCZ]~-
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The Vinyl Radical and Fluorinated Vinyl Radicals, C_2H_(3-n)F_n (n = 0-3), and Corresponding Anions: Comparison with the Isoelectronic Complexes [X···YCCZ]~-

机译：乙烯基自由基和氟化乙烯基自由基，C_2H_（3-n）F_n（n = 0-3）和相应的阴离子：与等电子配合物的比较[X···YCCZ]〜-

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Density functional theory (DFT) has been utilized to study the vinyl radical and fluorinated vinyl radical series, C_2H_(3-n)F_n, n = 0-3. Six different functionals-B3LYP, B3P86, BHLYP, BLYP, BP86, and LSDA-were used. A double-ζ basis set, augmented with additional s- and p-type diffuse functions as well as additional polarization functions (DZP++), was employed for all of the computations. Extensive calibrative studies have demonstrated that the DZP++ B3LYP, BLYP, and BP86 methods do a good job in the prediction of electron affinities. Neutral-anion energy separations were used to calculate the adiabatic electron affinities (EAad), the vertical electron affinities (EAvert), and the vertical detachment energies (VDE). These electron affinities were found to get progressively larger as the number of fluorines is increased; ZPVE-corrected values predicted by the reliable BLYP method are 0.66 eV (C_2H_3), 1.54 eV (C_2H_2F), 1.96 eV (C_2HF_2), and 2.40 eV (C_2F_3). This trend can be attributed to increasing anion stability, which can be rationalized in terms of inductive and negative hyperconjugative effects. Optimized geometries for all of the neutral and anionic species, which are indicative of the aforementioned effects, are presented. The 1-fluorovinyl radical is found to lie lowest in energy of the mono-fluorinated species, whereas the most stable anion of the same stoichiometry is a fluoride···acetylene complex, which is found to lie 19.5 kcal mol~(-1) lower than the 1-fluorovinyl anion using BLYP. The most stable configuration for the difluorinated species is 2,2-difluorovinyl for both the neutral radical and the anion.
机译：密度泛函理论（DFT）已用于研究乙烯基和氟化乙烯基系列C_2H_（3-n）F_n，n = 0-3。使用了六个不同的功能-B3LYP，B3P86，BHLYP，BLYP，BP86和LSDA。在所有计算中均采用了双ζ基集，并增加了其他s型和p型扩散函数以及其他极化函数（DZP ++）。广泛的校准研究表明，DZP ++ B3LYP，BLYP和BP86方法在预测电子亲和力方面做得很好。使用中性阴离子能量分离来计算绝热电子亲和力（EAad），垂直电子亲和力（EAvert）和垂直脱离能（VDE）。随着氟原子数量的增加，这些电子亲和力逐渐变大。通过可靠的BLYP方法预测的ZPVE校正值分别为0.66 eV（C_2H_3），1.54 eV（C_2H_2F），1.96 eV（C_2HF_2）和2.40 eV（C_2F_3）。这种趋势可以归因于阴离子稳定性的提高，可以根据诱导和消极的超共轭效应进行合理化处理。提出了所有中性和阴离子物种的优化几何结构，这些几何结构表明了上述效果。发现1-氟乙烯基自由基的能量是单氟化物质中最低的，而化学计量最稳定的阴离子是氟化物···乙炔络合物，发现其为19.5 kcal mol〜（-1）。低于使用BLYP的1-氟乙烯基阴离子。对于中性自由基和阴离子而言，二氟类物质最稳定的构型是2,2-二氟乙烯基。

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