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The effect of para substituents on the NC bond of aryl isocyanide molecules, adsorbed on Au, Ag, Pt and Pd surfaces were examined by vibrational sum frequency generation (VSFG) spectroscopy. The frequency of NC stretching vibration, υNC, depended on the electronic property of the substituents. When the substituents were more electron-withdrawing and more electron-donating, υNC shifted to lower and higher frequencies, respectively. However, υNC shifted to lower frequency again when the substituents were too electron-donating. The strong dependence of υNC on metal substrates was also observed, reflecting the difference in metal d-band energies, which leads to the difference in the contributions of σ-donation and π back donation the NC-metal coupling.

権利情報:

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  This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Mikio Ito, Hidenori Noguchi, Kohei Uosaki; Effect of para-substituents on NC bonding of aryl isocyanide molecules adsorbed on metal surfaces studied by sum frequency generation (SFG) spectroscopy. J. Chem. Phys. 21 November 2024; 161 (20): 204703 and may be found at (https://doi.org/10.1063/5.0236548.

キーワード: aryl isocyanide molecules, vibrational sum frequency generation, Hammett constant

刊行年月日: 2024-11-28

出版者: AIP Publishing

掲載誌:

• The Journal of Chemical Physics (ISSN: 00219606) vol. 161 issue. 20

研究助成金:

原稿種別: 著者最終稿 (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.5040

公開URL: https://doi.org/10.1063/5.0236548

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更新時刻: 2024-11-28 16:30:54 +0900

MDRでの公開時刻: 2024-11-28 16:30:54 +0900