Roaming

被引:114
作者
Bowman, Joel M. [1 ,2 ]
机构
[1] Emory Univ, Dept Chem, Atlanta, GA 30322 USA
[2] Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
关键词
roaming; methylnitrate dissociation; NO3; dissociation; reaction dynamics; POTENTIAL-ENERGY SURFACE; CLASSICAL TRAJECTORY CALCULATIONS; TRANSITION-STATES; THERMAL-DECOMPOSITION; UNIMOLECULAR DISSOCIATION; NITRITE REARRANGEMENT; REACTION-MECHANISM; REACTION DYNAMICS; SHOCK-TUBE; 248; NM;
D O I
10.1080/00268976.2014.897395
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In this review the roaming pathway in chemical reaction dynamics is described and illustrated. After a brief review and illustration of this pathway, an update on the chemical reactions where this pathway has been reported is given. Then the focus is on two recent systems where new aspects of roaming have been reported, namely roaming-isomerisation in CH3NO2 unimolecular dissociation and multi-electronic-state roaming in NO3 photodissociation. Full-dimensional potentials for these systems have been developed and used in quasiclassical trajectory calculations. Selected results from these studies are reviewed. So-called roaming saddle points and associated intrinsic reaction coordinate paths have been determined for these systems. These will be reviewed and investigated by making relevant comparisons with quasiclassical trajectories. Manifestations of roaming in quantum scattering and resonance calculations of the MgH + H Mg + H-2 reaction are reviewed. That is followed by a review of several statistical theories of roaming. The review concludes with some editorial' comments about the challenges that roaming presents to approximate theories and comments about possible future research directions.
引用
收藏
页码:2516 / 2528
页数:13
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