article published yes Yujing Wei author Liang Li author Julia E. Greenwald author Latha Venkataraman author 9ebb78a5-cc0d-11ee-8322-fae086a32caf0000-0002-6957-6089 Understanding how molecular geometry affects the electronic properties of single-molecule junctions experimentally has been challenging. Typically, metal–molecule–metal junctions are measured using a break-junction method where electrode separation is mechanically evolving during measurement. Here, to probe the impact of the junction geometry on conductance, we apply a sinusoidal modulation to the molecular junction electrode position. Simultaneously, we probe the nonlinearity of the current–voltage characteristics of each junction through a modulation in the applied bias at a different frequency. In turn, we show that junctions formed with molecules that have different molecule–electrode interfaces exhibit statistically distinguishable Fourier-transformed conductances. In particular, we find a marked bias dependence for the modulation of junctions where transmission is mediated thorough the van der Waals (vdW) interaction. We attribute our findings to voltage-modulated vdW interactions at the single-molecule level. American Chemical Society2023 eng 1530-6984 1530-6992 3660222110.1021/acs.nanolett.2c04098 232567-572 yes Y. Wei, L. Li, J.E. Greenwald, L. Venkataraman, Nano Letters 23 (2023) 567–572. Wei, Yujing, Liang Li, Julia E. Greenwald, and Latha Venkataraman. “Voltage-Modulated van Der Waals Interaction in Single-Molecule Junctions.” <i>Nano Letters</i>. American Chemical Society, 2023. <a href="https://doi.org/10.1021/acs.nanolett.2c04098">https://doi.org/10.1021/acs.nanolett.2c04098</a>. Wei, Y., Li, L., Greenwald, J. E., &#38; Venkataraman, L. (2023). Voltage-modulated van der waals interaction in single-molecule junctions. <i>Nano Letters</i>. American Chemical Society. <a href="https://doi.org/10.1021/acs.nanolett.2c04098">https://doi.org/10.1021/acs.nanolett.2c04098</a> Wei Y, Li L, Greenwald JE, Venkataraman L. Voltage-modulated van der waals interaction in single-molecule junctions. <i>Nano Letters</i>. 2023;23(2):567-572. doi:<a href="https://doi.org/10.1021/acs.nanolett.2c04098">10.1021/acs.nanolett.2c04098</a> Y. Wei, L. Li, J. E. Greenwald, and L. Venkataraman, “Voltage-modulated van der waals interaction in single-molecule junctions,” <i>Nano Letters</i>, vol. 23, no. 2. American Chemical Society, pp. 567–572, 2023. Wei, Yujing, et al. “Voltage-Modulated van Der Waals Interaction in Single-Molecule Junctions.” <i>Nano Letters</i>, vol. 23, no. 2, American Chemical Society, 2023, pp. 567–72, doi:<a href="https://doi.org/10.1021/acs.nanolett.2c04098">10.1021/acs.nanolett.2c04098</a>. Wei Y, Li L, Greenwald JE, Venkataraman L. 2023. Voltage-modulated van der waals interaction in single-molecule junctions. Nano Letters. 23(2), 567–572. 178652024-09-06T12:58:41Z2024-11-25T14:49:19Z