When Things Are Not as They Seem: Quantum Interference Turns Molecular Electron Transfer “Rules” Upside Down

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• 作者：Gemma C. Solomon ; David Q. Andrews ; Richard P. Van Duyne ; Mark A. Ratner
• 刊名：Journal of the American Chemical Society
• 出版年：2008
• 出版时间：June 25, 2008
• 年：2008
• 卷：130
• 期：25
• 页码：7788 - 7789
• 全文大小：402K
• 年卷期：v.130,no.25(June 25, 2008)
• ISSN：1520-5126

文摘

We present an interesting consequence of the differences between cross-conjugated and linearly conjugated molecules: the breakdown of conventional understanding of trends in molecular electron transfer. Interference effects are dominant in cross-conjugated molecules with unusual results: long molecules may have faster rates of electron transfer than short molecules, saturated molecules may have faster rates of electron transfer than conjugated molecules of the same length, and the rate of electron transfer cannot be correlated with energy gaps between the donor and acceptor states and the energy levels of the bridging molecule.