Single-molecule infrared spectroscopy with scanning tunneling microscopy

Probing vibrations at the single-molecule level is essential for achieving bond-specific chemical control. Here, we introduce a new measurement scheme that integrates frequency-tunable infrared excitation with scanning tunneling microscopy to characterize vibration-mediated nuclear motions of single molecules. We first validated the technique by monitoring the infrared-induced rotation of the ethynyl radical, and then applied it to pyrrolidine, mapping its conformational dynamics. The resulting broadband spectra captured fundamental vibrational modes together with rich overtone and combination bands inaccessible by conventional methods, confirmed with isotopic substitutions. Density functional theory calculations showed that delocalized modes coupled with pyrrolidine ring puckering drive the structural transition, revealing altered selection rules compared to traditional infrared spectroscopy. This new experimental platform enables probing of molecular vibrations and transformations wit..., , # Single-molecule infrared spectroscopy with scanning tunneling microscopy Dataset DOI: [10.5061/dryad.cfxpnvxmn](https://doi.org/10.5061/dryad.cfxpnvxmn) ## Data overview This dataset contains raw and processed data supporting the manuscript **“Single-molecule infrared spectroscopy with scanning tunneling microscopy”**. The study introduces **Infrared Integrated Scanning Tunneling Microscopy (IRiSTM)** to characterize vibration-mediated nuclear motions of **single molecules**—specifically **ethynyl radicals** and **pyrrolidine**—on a Cu(100) surface. Included materials: * **Raw STM scans**: Nanonis `.sxm` * **Processed vibrational action/switching spectra & occupation metrics**: `.xlsx` * **Origin project for photocurrent mapping**: `.opju` * **Two archives**: home-built software + point-by-point raw IRiSTM datasets (`.zip`) Files are organized primarily by **manuscript figure number** and can be interpreted independently using the definitions below. ## Contents * [File organiz...,在单分子水平上探测振动对于实现键特异性化学调控至关重要。本文提出一种全新的测量方案，将频率可调的红外激发技术与扫描隧道显微镜（scanning tunneling microscopy）相结合，用以表征单分子的振动介导核运动。我们首先通过监测乙炔基自由基的红外诱导旋转验证了该技术的有效性，随后将其应用于吡咯烷，绘制了其构象动力学图谱。所获得的宽带光谱不仅捕获了基频振动模式，还涵盖了传统方法难以获取的丰富泛频与组合频带，这一结果经同位素取代实验得到了验证。密度泛函理论（density functional theory）计算表明，与吡咯烷环褶皱耦合的离域模式驱动了结构转变，揭示出相较于传统红外光谱发生改变的选择定则。这一新型实验平台可实现对分子振动与转变的探测…… # 基于扫描隧道显微镜的单分子红外光谱技术 数据集DOI：[10.5061/dryad.cfxpnvxmn](https://doi.org/10.5061/dryad.cfxpnvxmn) ## 数据集概览 本数据集包含支撑论文《基于扫描隧道显微镜的单分子红外光谱技术》的原始与处理后数据。该研究提出了**红外集成扫描隧道显微镜（Infrared Integrated Scanning Tunneling Microscopy, IRiSTM）**技术，用以表征Cu(100)表面上单分子——乙炔基自由基与吡咯烷——的振动介导核运动。 包含的材料： * **原始STM扫描数据**：Nanonis软件生成的`.sxm`格式文件 * **处理后的振动动作/切换光谱与占据度指标**：`.xlsx`格式文件 * **光电流映射的Origin工程文件**：`.opju`格式文件 * **两个压缩包**：自制软件与逐点采集的原始IRiSTM数据集（`.zip`格式） 文件主要按照**论文插图编号**进行组织，可通过下述定义独立解读。 ## 内容说明 * [文件组织方式……]