Department of Chemistry, Biochemistry and Pharmaceutical Sciences, University of Bern, Freiestrasse 3, CH-3012Bern, Switzerland.
Quantum Technology Centre, Physics Department, Lancaster University, LancasterLA1 4YB, United Kingdom.
Acc Chem Res. 2023 Feb 7;56(3):322-331. doi: 10.1021/acs.accounts.2c00726. Epub 2023 Jan 24.
ConspectusDuring the past decade or so, research groups around the globe have sought to answer the question: "How does electricity flow through single molecules?" In seeking the answer to this question, a series of joint theory and experimental studies have demonstrated that electrons passing through single-molecule junctions exhibit exquisite quantum interference (QI) effects, which have no classical analogues in conventional circuits. These signatures of QI appear even at room temperature and can be described by simple quantum circuit rules and a rather intuitive magic ratio theory. The latter describes the effect of varying the connectivity of electrodes to a molecular core and how electrical conductance can be controlled by the addition of heteroatoms to molecular cores. The former describes how individual moieties contribute to the overall conductance of a molecule and how the overall conductance can change when the connectivities between different moieties are varied. Related circuit rules have been derived and demonstrated, which describe the effects of connectivity on Seebeck coefficients of organic molecules. This simplicity arises because when a molecule is placed between two electrodes, charge transfer between the molecule and electrodes causes the molecular energy levels to adjust, such that the Fermi energy () of the electrodes lies within the energy gap between the highest occupied molecular orbital and lowest unoccupied molecular orbital. Consequently, when electrons of energy pass through a molecule, their phase is protected and transport takes place via phase-coherent tunneling. Remarkably, these effects have been scaled up to self-assembled monolayers of molecules, thereby creating two-dimensional materials, whose room temperature transport properties are controlled by QI. This leads to new molecular design strategies for increasing the on/off conductance ratio of molecular switches and to improving the performance of organic thermoelectric materials. In particular, destructive quantum interference has been shown to improve the Seebeck coefficient of organic molecules and increase their on/off ratio under the influence of electrochemical gating. The aim of this Account is to introduce the novice reader to these signatures of QI in molecules, many of which have been identified in joint studies involving our theory group in Lancaster University and experimental group in Bern University.
概述
在过去的十年左右,全球的研究团队一直在努力回答一个问题:“电子如何在单个分子中流动?”为了回答这个问题,一系列理论和实验联合研究表明,通过单分子结的电子表现出精细的量子干涉(QI)效应,这在传统电路中没有类似的经典模拟。这些 QI 的特征甚至在室温下也很明显,可以用简单的量子电路规则和相当直观的魔术比率理论来描述。后者描述了改变分子核心与电极的连接性的效果,以及如何通过向分子核心添加杂原子来控制电导率。前者描述了各个部分如何对分子的整体电导率做出贡献,以及当不同部分之间的连接性发生变化时,整体电导率如何变化。已经得出并证明了相关的电路规则,这些规则描述了连接性对有机分子的塞贝克系数的影响。这种简单性源于当分子置于两个电极之间时,分子和电极之间的电荷转移导致分子能级调整,使得电极的费米能()落在最高占据分子轨道和最低未占据分子轨道之间的能隙内。因此,当能量为 的电子通过分子时,它们的相位受到保护,并且通过相位相干隧穿进行输运。值得注意的是,这些效应已经扩展到分子的自组装单层,从而创造了二维材料,其室温输运性质受 QI 控制。这为增加分子开关的导通/关断电导率比和提高有机热电材料的性能提供了新的分子设计策略。特别是,已经表明破坏性量子干涉可以提高有机分子的塞贝克系数,并在电化学门控的影响下增加其导通/关断比。本文的目的是向新手读者介绍分子中的这些 QI 特征,其中许多特征是在兰卡斯特大学的理论小组和伯尔尼大学的实验小组的联合研究中确定的。
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