乙的臭氧分解 - - 一个量子化学研究
D Cremer1, R Crehuet, J Anglada
1Department of Theoretical Chemistry, Göteborg University, Reutersgatan 2, S-41320 Göteborg, Sweden.
Journal of the American Chemical Society
|June 21, 2001
概括
乙的臭氧分解涉及由循环添加启动的复杂反应机制,形成快速重新排列的关键中间体. 进一步的转化产生各种产品,如formmanhydride和glyoxal.
科学领域:
- * 计算化学 计算化学
- * 大气中的化学成分
- * * 反应机制的反应机制
背景情况:
- *臭氧溶解是重要的大气反应途径.
- * 了解乙烯臭氧分解可以了解复杂的化学过程.
研究的目的:
- * 为了阐明乙氧化溶解的反应机制.
- * 调查关键中间体的能量和路径.
主要方法:
- *高层次的初始计算:带有单次和双次激发的合集群 (CCSD(T)) 和完整的活性空间二次扰动理论 (CASPT2).
- *密度函数理论 (DFT) 使用B3LYP函数.
- * 用6-311+G(2d,2p) 基数为所有计算.
主要成果:
- * 反应通过 [4pi + 2pi] 循环添加形成1,2,3-三烯,计算激活值为9.6 kcal/mol.
- * 关键的中间体,α-ketocarbonyl氧化物 (5),经历异构和循环,形成各种化合物,包括二氧化 (19),三氧化[2.1.0] (10),氧化 (15),和二氧化 (9).
- *这些中间体分解或重新排列,产生曼化物,酸,甲,酸和酸作为主要产品.
结论:
- *乙烯臭氧分解通过复杂的多步骤机制进行.
- *计算的激活度提供了反应途径的详细能量概况.
- *这些发现强调了需要进一步实验验证拟议机制的必要性.
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