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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Energetics and Structures of the Carbonyl Chloride Radical, Oxalyl Chloride, and Their Cations
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Energetics and Structures of the Carbonyl Chloride Radical, Oxalyl Chloride, and Their Cations

机译：羰基氯自由基，草酰氯及其阳离子的能级和结构

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An ab initio study on the structures and energetics of the carbonyl chloride radical and its dimer, oxalyl chloride, along with their cations, was carried out using the Gaussian-2 (G2) and Gaussian-3 (G3) models of theory. The structural results obtained include optimized geometries of ClCO, ClCO~+, the anti, syn, and gauche conformers of (ClCO)_2 and the transition structure (TS) connecting the anti and gauche conformers, and (ClCO)_2~+. The energetic results reported include the heats of formation for ClCO, various (ClCO)_2 conformers and transition structures, ClCO~+, and (ClCO_2~+, as well as the adiabatic and vertical ionization energies of ClCO and (ClCO)_2. The G3 results obtained are in very good agreement with the available experimental data. In some cases, where the experimental data are unavailable or imprecise, the G3 results should be reliable estimates. Among the three experimental #DELTA#H_(f298) deg values for ClCO found in the literature, the one most recently reported (-21.8 +- 2.5 kJ mol~(-1) has the best agreement with the G3 result (-19.4 kJ mol~(-1)). For oxalyl chloride, we located a gauche conformer and a TS linking the anti and gauche conformers at the MP2(Full)/6-311+G(3df,2p) level, in qualitative agreement with the experimental findings. Also, both experimental and computational results agree that both the anti and gauche conformers lie in very flat potential minima. Based on the limited number of systems studied in this work, the G3 model yields results which are in better agreement with the experimental data than the G2 method.
机译：使用理论模型Gaussian-2（G2）和Gaussian-3（G3）从头开始研究了羰基氯自由基及其二聚体草酰氯及其阳离子的结构和能量。获得的结构结果包括优化的ClCO，ClCO〜+几何构型，（ClCO）_2的反，顺式和gauche构象异构体以及连接反和gauche构象的过渡结构（TS）和（ClCO）_2〜+。报告的高能结果包括ClCO的形成热，各种（ClCO）_2构象异构体和过渡结构，ClCO〜+和（ClCO_2〜+）以及ClCO和（ClCO）_2的绝热和垂直电离能。 G3的结果与可用的实验数据非常吻合，在某些情况下，如果实验数据不可用或不精确，则G3的结果应该是可靠的估计值在三个实验中ClCO的＃DELTA＃H_（f298）deg值中在文献中发现，最近报道的一种（-21.8 +-2.5 kJ mol〜（-1）与G3结果（-19.4 kJ mol〜（-1））具有最佳的一致性。对于草酰氯，我们找到了gauche构象构象和TS在MP2（Full）/ 6-311 + G（3df，2p）水平上连接反构象和gauche构象构象，与实验结果在质量上是一致的，而且，实验和计算结果都同意和gauche符合者处于极低的电位最小值。在这项工作中研究的系统中，与G2方法相比，G3模型产生的结果与实验数据更加吻合。

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