当前位置: X-MOL 学术Chem. Phys. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
Adjacent keto and enol groups in photochemistry of a cyclic molecule: Products, mechanisms and dynamics
Chemical Physics ( IF 2.3 ) Pub Date : 2018-07-30 , DOI: 10.1016/j.chemphys.2018.07.045
Dorit Shemesh , Ronnie Salomon , Stephanie Hyejin Kim , Geoffrey S. Tyndall , Sergey A. Nizkorodov , R. Benny Gerber

The photochemistry of carbonyl compounds is of considerable atmospheric importance, but the mechanisms and dynamics are often unknown. Here, we explore these topics for a system with adjacent keto and enol chromophoric groups. The photochemistry in the S1 and S2 states of the most stable tautomer of 1,2-cyclohexanedione, is studied theoretically using molecular dynamics simulations with a semi-empirical excited-state potential. Results are compared with experiments. The main results are: (1) Calculations provide an interpretation of the measured absorption spectrum. (2) There is good agreement between the predicted and experimental photoproducts. (3) Agreement with experiments on the products suggests the latter can be predicted without treating non-adiabatic transitions. (4) The mechanisms of formation of the products are predicted by the simulations. (5) The adjacent keto-enol system is found to be photochemically very different from the pure keto one.



中文翻译:

环状分子光化学中的相邻酮基和烯醇基团:产品,机理和动力学

羰基化合物的光化学在大气中具有重要意义,但是其机理和动力学通常是未知的。在这里,我们探索具有相邻的酮基和烯醇发色基团的系统的这些主题。S 1和S 2中的光化学理论上使用具有半经验激发态电势的分子动力学模拟研究了最稳定的1,2-环己二酮互变异构体的分子状态。将结果与实验进行比较。主要结果是:(1)计算提供了对测得的吸收光谱的解释。(2)预测的和实验的光产品之间有很好的一致性。(3)与产品实验的一致性表明,无需处理非绝热转变,就可以预测后者。(4)通过模拟预测了产物的形成机理。(5)发现相邻的酮-烯醇体系在光化学上与纯酮体系大不相同。

更新日期:2018-12-05
down
wechat
bug