Single-Molecule Vibrational Characterization of Binding Geometry Effects on Isocyanide-Metal Interactions
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arXiv
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| Main Authors: | , , , , , , , |
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| Format: | Preprint |
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2025
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| _version_ | 1866908302730854400 |
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| author | Bi, Liya Wang, Zhe Balto, Krista Tao, Andrea R. Pascal, Tod A. Zhang, Yanning Figueroa, Joshua S. Li, Shaowei |
| author_facet | Bi, Liya Wang, Zhe Balto, Krista Tao, Andrea R. Pascal, Tod A. Zhang, Yanning Figueroa, Joshua S. Li, Shaowei |
| contents | Isocyanide-metal binding is governed by sigma-donation and pi-back-bonding, which affects the energy of the isocyanide stretching mode-a characteristic probe for ligand-metal interactions. While extensive correlations exist between structure and spectroscopy in molecular isocyanide-metal systems, isocyanide interactions with metallic crystalline surfaces, where ligands often bind in various geometries, remain poorly understood. Conventional vibrational spectroscopies, such as infrared and Raman, lack the molecular-scale resolution needed to distinguish these inhomogeneous configurations. In contrast, inelastic electron tunneling spectroscopy with scanning tunneling microscopy (STM-IETS) enables direct visualization of ligand adsorption geometries and their vibrational signatures. Using STM-IETS, here we investigate a matal-adsorbed m-terphenyl isocyanie ligand and find that adsorption geometry on Cu(100) induces a significant shift in isocyanide stretching frequency, even greater than replacing Cu(100) with Ag(111). Density functional theory confirms this shift arises from atomic-scale variations in isocyanide-metal binding. This study elucidates how atomic-scale binding influences the vibrational signatures of isocyanide ligands-an often-overlooked factor in understanding isocyanide-metal interactions. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2504_03945 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Single-Molecule Vibrational Characterization of Binding Geometry Effects on Isocyanide-Metal Interactions Bi, Liya Wang, Zhe Balto, Krista Tao, Andrea R. Pascal, Tod A. Zhang, Yanning Figueroa, Joshua S. Li, Shaowei Mesoscale and Nanoscale Physics Isocyanide-metal binding is governed by sigma-donation and pi-back-bonding, which affects the energy of the isocyanide stretching mode-a characteristic probe for ligand-metal interactions. While extensive correlations exist between structure and spectroscopy in molecular isocyanide-metal systems, isocyanide interactions with metallic crystalline surfaces, where ligands often bind in various geometries, remain poorly understood. Conventional vibrational spectroscopies, such as infrared and Raman, lack the molecular-scale resolution needed to distinguish these inhomogeneous configurations. In contrast, inelastic electron tunneling spectroscopy with scanning tunneling microscopy (STM-IETS) enables direct visualization of ligand adsorption geometries and their vibrational signatures. Using STM-IETS, here we investigate a matal-adsorbed m-terphenyl isocyanie ligand and find that adsorption geometry on Cu(100) induces a significant shift in isocyanide stretching frequency, even greater than replacing Cu(100) with Ag(111). Density functional theory confirms this shift arises from atomic-scale variations in isocyanide-metal binding. This study elucidates how atomic-scale binding influences the vibrational signatures of isocyanide ligands-an often-overlooked factor in understanding isocyanide-metal interactions. |
| title | Single-Molecule Vibrational Characterization of Binding Geometry Effects on Isocyanide-Metal Interactions |
| topic | Mesoscale and Nanoscale Physics |
| url | https://arxiv.org/abs/2504.03945 |