Excited-State Deactivation Pathways in Uracil versus Hydrated Uracil: Solvatochromatic Shift in the 1nπ* State is the Key
作者： Xing Zhang , John M. Herbert
DOI: 10.1021/JP412092F
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摘要: Excited-state deactivation mechanisms of uracil are investigated using spin-flip time-dependent density functional theory. Two important minimum-energy crossing points located, for both gas-phase and hydrated uracil, optimized relaxation pathways connecting the most critical on 1nπ* 1ππ* potential energy surfaces determined. An ultrafast decay time constant, measured via femtosecond spectroscopy, is assigned to direct → S0 deactivation, while a slower component indirect deactivation. The shorter lifetime dark state in aqueous solution attributed decrease barrier along pathway minimum 1ππ*/S0 conical intersection. This arises due hydrogen bonding between water, leading blue-shift excitation considerable modification barriers surface. These results illustrate how t...
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