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半花菁类非绝热紫外保护机理的超快光谱研究

Ultrafast Spectroscopic Study on Non-adiabatic UV Protection Mechanism of Hemicyanines

  • 摘要: 本文首次结合理论计算与瞬态吸收光谱,阐明了典型的半花菁类化合物Hemicy和Dhemicy的紫外光防护动力学机理. 理论和实验证明,Hemicy和Dhemicy在UVC、UVB和UVA区域都有很强的吸收能力. Hemicy和Dhemicy吸收能量后跃迁到激发态. Hemicy和Dhemicy在S _1 态和S _0 态势能曲线的圆锥交点处,经历从S _1 态到S _0 态的非绝热弛豫和顺式反异构化光物理过程. 瞬态吸收光谱表明反式-顺式光异构化过程将在几皮秒内发生. 因此,通过非绝热反式-顺式光异构化过程快速地弛豫掉Hemicy和Dhemicy吸收的能量.

     

    Abstract: In this work, we firstly elucidated the ultraviolet light protection dynamics mechanism of the typical hemicyanines, i.e.. Hemicy and DHemicy, by combining the theoretical calculation method and the transient absorption spectra. It is theoretically and experimentally demonstrated that both Hemicy and DHemicy have strong absorption in UVC (200-280 nm), UVB (280-300 nm), and UVA (320-400 nm) regions. Moreover, after absorbing energy, Hemicy and DHemicy can jump into the excited states. Subsequently, Hemicy and DHemicy relax to \mathrmS_0 states from \mathrmS_1 states rapidly by the non-adiabatic transition at the conical intersection point between the potential energy curves of \mathrmS_1 and \mathrmS_0 states, and are accompanied by the trans-cis photoisomerism. The transient absorption spectra show that trans-cis photoisomerization occur within a few picoseconds. Thus, the ultraviolet energy absorbed by Hemicy and DHemicy could be relaxed ultrafastly by the non-adiabatic trans-cis photoisomerization processes.

     

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