Effects of electrolyte gating on single-molecule electronic transport

尽管取得了显著的成果，分子电子学仍然面临着主要的困难，如：例如，在一个实施例中，通过栅电极有效控制单分子传输。最近的传输实验证明了电解质门控的重要实用优势。在这一领域的进展需要超越目前使用的现象学Newns-Anderson框架，其中的氧化还原单元被建模为一个点状的单占据能级，和溶剂作为一个经典的振荡器的理论理解。在与Wandlowski教授（伯尔尼）的实验组的密切合作下，我们将首次发展电解质中绝热输运的微观理论，该理论将逐步完善，以接近真空电子学理论的水平。在第一步中，我们将进行量子力学/分子力学计算，以微观上考虑内部和外部弛豫，以及多MO（分子轨道）不相关的氧化还原单元。基本上，这是大多数真空电子学研究的理论水平。氧化还原的电子结构将在从头算方法中进一步细化，该方法消除了DFT的物理模糊性-“轨道”，并准确地解释了电子相关性。此外，我们将完善内氧化还原弛豫，这是重要的电解质门控的描述。该项目的实现将为电解质中分子输运的微观理解提供新的理论背景。

In spite of significant results, molecular electronics remains confronted with major difficulties, e. g., the efficient control of the single-molecule transport via a gate electrode. Recent transport experiments demonstrated important practical advantages of the electrolyte gating. Advances in this field require a theoretical understanding beyond the presently used phenomenological Newns-Anderson framework, wherein the redox unit is modeled as a point-like singly occupied energy level, and the solvent as a classical oscillator. In close cooperation with the experimental group of Professor Wandlowski (Bern), we will develop for the first time a microscopic theory of the adiabatic transport in electrolytes, which will be refined in a stepwise fashion to approach the level of vacuum electronics theory. In the first step, we will perform quantum-mechanical/molecular mechanics calculations to microscopically account both for the inner and the outer relaxation, and a multi-MO (molecular orbital) uncorrelated redox unit. Basically, this is the theoretical level of most studies in vacuum electronics. The redox’ electronic structure will be next refined within an ab initio approach, which eliminates the physical ambiguity of the DFT-”orbitals” and accurately accounts for electron correlations. Further, we will refine the description of the intra-redox relaxation, which is important for the electrolyte gating. The realization of this project will generate a novel theoretical context for the microscopical understanding of the molecular transport in electrolytes.