Electron-diffraction investigations of gaseous sulphur dioxide and trioxide

A. Clark, B. Beagley
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引用次数: 41

Abstract

Electron-diffraction intensity data have been collected for gaseous sulphur dioxide (250 K) and rioxide (300 K) at camera lengths of 50 and 25 cm. Least squares refinement led to the following ra distances, root-mean-square amplitudes of vibration, and estimated standard deviations; for SO2, rS–O= 1.431 ± 0.002 A, rO‥O= 2.460±0.012 A, uS–O= 0.041±0.003 A, and uO‥O= 0.053±0.012 A, for SO3, rS–O= 1.418±0.003 A, rO‥O= 2.457±0.009 A, uS–O= 0.048±0.005 A and uO‥O= 0.067±0.010 A. The corresponding value for the angle in the dioxide is 118.5±1.0°, whilst the trioxide is planar within experimental error. For both molecules, spectroscopic estimates of the vibrational amplitudes have been made from force-constant data, and for SO2 these are in satisfactory agreement with the diffraction results. For SO3, however, agreement is poorer and this may indicate the presence of a small amount of S3O9 trimer in the diffracting vapour. Mean-square parallel and perpendicular amplitudes of vibration and centrifugal distortion corrections have also been calculated for both molecules and the electron-diffraction ra parameters converted to equilibrium (re), and zero-point-average (r°α), values. For SO2, these structures differ insignificantly from corresponding microwave re and rz estimates.
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气态二氧化硫和三氧化物的电子衍射研究
在相机长度为50和25厘米处,收集了气态二氧化硫(250 K)和氧化物(300 K)的电子衍射强度数据。最小二乘细化得到以下ra距离、振动的均方根振幅和估计的标准差;对于SO2, rS-O = 1.431±0.002 A, rO…n = 2.460±0.012 A, uS-O = 0.041±0.003 A,和uO…n = 0.053±0.012 A,对于SO3, rS-O = 1.418±0.003 A, rO…n = 2.457±0.009 A, uS-O = 0.048±0.005 A和uO…n = 0.067±0.010 A。在实验误差范围内,二氧化二氮的角度对应值为118.5±1.0°,而三氧化二氮为平面。对于这两种分子,振动振幅的光谱估计已经从力常数数据中得到,对于SO2,这与衍射结果是令人满意的。然而,对于SO3,一致性较差,这可能表明在衍射蒸汽中存在少量的S3O9三聚体。还计算了分子的均方平行和垂直振动振幅和离心畸变校正,并将电子衍射参数转换为平衡(re)和零点平均(r°α)值。对于SO2,这些结构与相应的微波re和rz估计值差别不大。
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