Dynamics of excited state electron transfer at a liquid interface using time-resolved sum frequency generation

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• 作者：Yi Rao ; Man Xu ; Steffen Jockusch ; Nicholas J. Turro ; Kenneth B. Eisenthal
• 刊名：Chemical Physics Letters
• 出版年：2012
• 出版时间：20 August, 2012
• 年：2012
• 卷：544
• 期：Complete
• 页码：1-6
• 全文大小：610 K

文摘

Femtosecond time resolved vibrational sum frequency generation has been used for the first time to probe a chemical reaction involving interfacial molecules pumped into their excited electronic states. The ultrafast dynamics of electron transfer from ground state N,N-dimethylaniline (DMA) to photoexcited coumarin 314 at a water/DMA monolayer interface was obtained. The forward electron transfer time constant is 16 ¡À 2 ps, which is faster than electron transfer in bulk DMA. The faster rate is attributed to a lower reorganization free energy, which is a consequence of lower interfacial polarity. The back electron transfer time constant is 174 ¡À 21 ps.