Rotational resonances in the H<sub>2</sub>CO roaming reaction are revealed by detailed correlations

doi:10.1126/science.abc4088

GSTDTAP > 气候变化

DOI	10.1126/science.abc4088
	Rotational resonances in the H₂CO roaming reaction are revealed by detailed correlations
	Mitchell S. Quinn; Klaas Nauta; Meredith J. T. Jordan; Joel M. Bowman; Paul L. Houston; Scott H. Kable
	2020-09-25
发表期刊	Science
出版年	2020
英文摘要	The phenomenon of roaming in chemical reactions (that is, bypassing the minimum energy pathway from unlikely geometries) has attracted a great deal of attention in the chemical reaction dynamics community over the past decade and still demonstrates unexpected results. Using velocity-map imaging of state-selected H2 products of H2CO photodissociation, Quinn et al. discovered the bimodal structure of rotational distribution of the other product fragment, CO. Quasiclassical trajectories showed that this bimodality originates from two distinctive reaction pathways that proceed by the trans or cis configuration of O–C–H⋯H, leading to high or low rotational excitations of CO, respectively. Whether such a mechanism is present in the many other chemical reactions for which roaming reaction pathways have been reported is yet to be determined. Science , this issue p. [1592][1] Since its discovery 16 years ago, roaming has become a ubiquitous mechanism in molecular photochemistry. Its general features are now understood, but little detail is known about how the potential energy surface (PES) determines reaction outcomes. We performed detailed experiments on formaldehyde (H2CO) photodissociation and determined fully correlated quantum state distributions of the molecular hydrogen and carbon monoxide products. These experiments reveal previously undetected bimodal carbon monoxide rotational distributions. Insights from classical trajectory calculations demonstrate that these features arise from resonances as the PES directs the reaction into cis and trans O–C–H···H critical geometries, which produce rebound and stripping mechanisms, respectively. These subtle and pervasive effects demonstrate additional complexity in this prototypical roaming reaction, which we expect to be general. They also provide detailed benchmarks for predictive theories of roaming. [1]: /lookup/doi/10.1126/science.abc4088
领域	气候变化 ; 资源环境
URL	查看原文
引用统计	被引频次：23[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://119.78.100.173/C666/handle/2XK7JSWQ/296502
专题	气候变化资源环境科学
推荐引用方式 GB/T 7714	Mitchell S. Quinn,Klaas Nauta,Meredith J. T. Jordan,et al. Rotational resonances in the H₂CO roaming reaction are revealed by detailed correlations[J]. Science,2020.
APA	Mitchell S. Quinn,Klaas Nauta,Meredith J. T. Jordan,Joel M. Bowman,Paul L. Houston,&Scott H. Kable.(2020).Rotational resonances in the H₂CO roaming reaction are revealed by detailed correlations.Science.
MLA	Mitchell S. Quinn,et al."Rotational resonances in the H₂CO roaming reaction are revealed by detailed correlations".Science (2020).