Abstract Hydrogen(H)-bond dynamics are involved in many elementary processes in chemistry and biology. Because of its fundamental importance, a variety of experimental and theoretical approaches have been employed to study the dynamics in gas, liquid, solid phases, and their interfaces. This review describes the recent progress of direct observation and control of H-bond dynamics in several model systems on a metal surface by using low-temperature scanning tunneling microscopy (STM). General aspects of H-bond dynamics and the experimental methods are briefly described in chapter 1 and 2. In the subsequent four chapters, I present direct observation of an H-bond exchange reaction within a single water dimer (chapter 3), a symmetric H bond (chapter 4) and H-atom relay reactions (chapter 5) within water–hydroxyl complexes, and an intramolecular H-atom transfer reaction (tautomerization) within a single porphycene molecule (chapter 6). These results provide novel microscopic insights into H-bond dynamics at the single-molecule level, and highlight significant impact on the process from quantum effects, namely tunneling and zero-point vibration, resulting from the small mass of H atom. Additionally, local environmental effect on H-bond dynamics is also examined by using atom/molecule manipulation with the STM.

中文翻译：

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使用低温扫描隧道显微镜直接观察和控制氢键动力学

摘要 氢（H）键动力学涉及化学和生物学的许多基本过程。由于其根本重要性，各种实验和理论方法已被用于研究气、液、固相及其界面的动力学。这篇综述描述了使用低温扫描隧道显微镜 (STM) 在金属表面的几个模型系统中直接观察和控制氢键动力学的最新进展。第 1 章和第 2 章简要描述了氢键动力学的一般方面和实验方法。在随后的四章中，我将直接观察单个水二聚体（第 3 章）内的氢键交换反应，对称 H水-羟基配合物中的键（第 4 章）和 H 原子中继反应（第 5 章），以及单个卟啉分子内的分子内 H 原子转移反应（互变异构化）（第 6 章）。这些结果为单分子水平的氢键动力学提供了新的微观见解，并突出了量子效应对过程的重大影响，即由于氢原子质量小而产生的隧道效应和零点振动。此外，还通过使用 STM 的原子/分子操作来检查局部环境对 H 键动力学的影响。