First-principles simulation of a photoinduced carbocation formation

详细信息	查看全文 | 推荐本文 |

• 作者：J. Friedrichs ; D.J. Coughtrie ; I. Frank ; ^{irmgard.frank@theochem.uni-hannover.de}
• 关键词：Carbocations ; Density-functional calculations ; First-principles molecular dynamics ; Photochemical reaction ; Reaction mechanism
• 刊名：Chemical Physics
• 出版年：2012
• 期刊代码：18_03010104
• 类别：ch
• 出版时间：19 June, 2012
• 卷：402
• 期：Complete
• 页码：69-73
• 文件大小：957 K

摘要

The photodissociation of diphenylmethyl chloride (DPMCl) can lead to the formation of radicals or ions depending on the environment. We use first-principles molecular dynamics simulations to study the photochemistry of DPMCl in the gas phase and in aqueous solution. In the gas phase simulations the photoexcitation leads to the formation of a radical pair. For the photoreaction of DPMCl in a polar solution a two-step process is observed: the actual photoreaction proceeds diabatically and leads to the formation of a radical pair. This radical pair is subsequently transformed into an ion pair via an electron transfer reaction. The ultrafast process explains the experimentally observed formation of ions on a sub-picosecond timescale.