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Molecular Photofragmentation Dynamics in the Gas and Condensed Phases
Annual Review of Physical Chemistry ( IF 14.7 ) Pub Date : 2017-05-02 00:00:00 , DOI: 10.1146/annurev-physchem-052516-050756
Michael N.R. Ashfold 1 , Daniel Murdock 1 , Thomas A.A. Oliver 1
Affiliation  

Exciting a molecule with an ultraviolet photon often leads to bond fission, but the final outcome of the bond cleavage is typically both molecule and phase dependent. The photodissociation of an isolated gas-phase molecule can be viewed as a closed system: Energy and momentum are conserved, and the fragmentation is irreversible. The same is not true in a solution-phase photodissociation process. Solvent interactions may dissipate some of the photoexcitation energy prior to bond fission and will dissipate any excess energy partitioned into the dissociation products. Products that have no analog in the corresponding gas-phase study may arise by, for example, geminate recombination. Here, we illustrate the extent to which dynamical insights from gas-phase studies can inform our understanding of the corresponding solution-phase photochemistry and how, in the specific case of photoinduced ring-opening reactions, solution-phase studies can in some cases reveal dynamical insights more clearly than the corresponding gas-phase study.

中文翻译:


气相和冷凝相中的分子光碎裂动力学

用紫外线光子激发分子通常会导致键裂,但键断裂的最终结果通常取决于分子和相位。分离出的气相分子的光解离可以看作是一个封闭的系统:能量和动量得以守恒,并且碎裂是不可逆的。在溶液相光解离过程中并非如此。溶剂相互作用可在键裂变之前消散一些光激发能,并消散分配到离解产物中的任何多余能量。在相应的气相研究中没有类似物的产物可能会通过,例如,重组发生。在这里,我们说明了气相研究的动态洞察力在多大程度上可以帮助我们理解相应的溶液相光化学以及如何,

更新日期:2017-05-02
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