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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Conformational Stability of 3-Fluoropropene in Rare Gas Solutions from Temperature-Dependent FT-IR Spectra and ab Initio Calculations
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Conformational Stability of 3-Fluoropropene in Rare Gas Solutions from Temperature-Dependent FT-IR Spectra and ab Initio Calculations

机译：取决于温度的FT-IR光谱和从头算的稀有气体溶液中3-氟丙烯的构象稳定性

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摘要

The infrared spectra (3500-400 cm~(-1)) of 3-fluoropropene (allyl fluoride), CH_2=C(H)CH_2F, dissolved in liquid argon, krypton, and xenon have been recorded at various temperatures ranging from -180 to -65 deg C. From these studies, the enthalpy difference between the more stable cis conformer and the high-energy gauche rotamer has been determined to range from 60 +- 8 cm~(-1) (718 +- 96 J/mol) in liquid xenon to 81 +- 1 cm~(-1) (969 +- 12 J/mol) in liquid argon. These values have been extrapolated utilizing a linear relationship between the Kirkwood function of the solvent and the enthalpy differences in the solvents to give a value of 130 +- 25 cm~(-1) (1.56 +- 0.30 kJ/mol) for the vapor. From the experimental enthalpy value, the gauche dihedral angle, torsional transitions for both rotamers, and better structural parameters, the potential function governing the conformational interchange has been recalculated. Ab initio calculations utilizing the 6-31G(d,p) and 6-311G(d,p) basis sets with electron correlation at the MP2 level predict the cis conformer to be the more stable rotamer, but from the MP2/6-311++G(d,p) calculation the gauche conformer is predicted to the more stable by 117 cm~(-1) (1.40 kJ/mol). By combination of the ab initio initio predictions of the structural parameters with the previously reported microwave rotational constants for 11 different isotopic species of both conformers, complete r_o parameters have been obtained for both rotamers. The results of these structural parameter determinations are compared to those previously reported.
机译：在-180范围内的各种温度下记录了溶解在液态氩，rypto和氙中的3-氟丙烯（烯丙基氟），CH_2 = C（H）CH_2F的红外光谱（3500-400 cm〜（-1））至-65摄氏度。根据这些研究，更稳定的顺式构象异构体和高能薄纱旋转异构体之间的焓差已确定为60 +-8 cm〜（-1）（718 +-96 J / mol ）在液态氙中达到81±1 cm〜（-1）（969±12 J / mol）在液态氩中。利用溶剂的柯克伍德函数和溶剂的焓差之间的线性关系来推断这些值，从而得出蒸气的值为130 +-25 cm〜（-1）（1.56 +-0.30 kJ / mol） 。从实验焓值，纱罗二面角，两个旋转异构体的扭转转变以及更好的结构参数，已经重新计算了控制构象互换的潜在函数。使用6-31G（d，p）和6-311G（d，p）基集以及在MP2级别具有电子相关性的从头算计算可以预测顺式构象异构体更稳定，但是从MP2 / 6-311出发++ G（d，p）计算可预测auche构象构象更稳定，达到117 cm〜（-1）（1.40 kJ / mol）。通过将结构参数的从头算起的预测与先前报道的两种构象异构体的11种不同同位素的微波旋转常数相结合，已经获得了两种旋转异构体的完整r_o参数。将这些结构参数确定的结果与先前报告的结果进行比较。

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