Effect of para-substituents on NC bonding of aryl isocyanide molecules adsorbed on metal surfaces studied by sum frequency generation (SFG) spectroscopy.

IF 3.1 2区 化学 Q3 CHEMISTRY, PHYSICAL
Mikio Ito, Hidenori Noguchi, Kohei Uosaki
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引用次数: 0

Abstract

The effect of para-substituents on the NC bond of aryl isocyanide molecules adsorbed on Au, Ag, Pt, and Pd surfaces was 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 of the NC-metal coupling.

利用总频发生(SFG)光谱学研究对位取代基对吸附在金属表面的芳基异氰酸酯分子 NC 键的影响。
通过振动总频发生(VSFG)光谱法研究了对位取代基对吸附在金、银、铂和钯表面的芳基异氰酸酯分子的 NC 键的影响。NC 伸展振动的频率 υNC 取决于取代基的电子特性。当取代基的吸电子性和携电子性较强时,υNC 分别向较低和较高的频率移动。然而,当取代基过于疏电子时,υNC 又转向较低频率。还观察到υNC 对金属基质的强烈依赖性,这反映了金属 d 带能量的差异,从而导致 NC 金属耦合的 σ 供电子和 π 反供电子贡献的差异。
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来源期刊
Journal of Chemical Physics
Journal of Chemical Physics 物理-物理:原子、分子和化学物理
CiteScore
7.40
自引率
15.90%
发文量
1615
审稿时长
2 months
期刊介绍: The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance. Topical coverage includes: Theoretical Methods and Algorithms Advanced Experimental Techniques Atoms, Molecules, and Clusters Liquids, Glasses, and Crystals Surfaces, Interfaces, and Materials Polymers and Soft Matter Biological Molecules and Networks.
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