Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, Ohio 45221-0172, USA.
J Phys Chem A. 2010 Mar 4;114(8):2799-805. doi: 10.1021/jp912253t.
Matrix isolation studies combined with infrared spectroscopy of the twin jet codeposition of ozone and cis-2-butene into argon matrices have led to the first observation of several early intermediates in this ozonolysis reaction. Specifically, evidence is presented for the formation and identification of the long sought-after Criegee intermediate, as well as confirming evidence for earlier reports of the primary and secondary ozonides. These species were observed after initial twin jet deposition, and grew upon annealing to 35 K. Extensive isotopic labeling ((18)O and (16,18)O mixtures) experiments provided important supporting data. Detailed theoretical calculations at the B3LYP/6-311++G(d,2p) level were carried out as well to augment the experimental work. Merged jet (flow reactor) experiments followed by cryogenic trapping in solid argon led to the formation of "late", stable oxidation products. Photochemical reactions of ozone with cis-2-butene was studied as well, as was the photochemical behavior of the primary and secondary ozonides.
矩阵隔离研究结合臭氧和顺-2-丁烯在氩基质中双喷射共沉积的红外光谱分析，首次观察到该臭氧化反应中的几个早期中间体。具体而言，本文提出了长时寻求的 Criegee 中间体的形成和鉴定的证据，以及对早期报道的初级和次级臭氧化物的确认证据。这些物质在初始双喷射沉积后被观察到，并在退火至 35 K 时生长。广泛的同位素标记 ((18)O 和 (16,18)O 混合物) 实验提供了重要的支持数据。还进行了详细的理论计算，即在 B3LYP/6-311++G(d,2p) 水平上进行，以补充实验工作。随后进行的合并射流（流动反应器）实验，以及在固态氩中低温捕获，导致了“晚期”稳定氧化产物的形成。臭氧与顺-2-丁烯的光化学反应也进行了研究，以及初级和次级臭氧化物的光化学行为。
