1. Coupling Interfacial Electrochemistry with Nuclear Magnetic Resonance Spectroscopy: An Electronic Perspective
- Author
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Yu Ye Tong
- Subjects
symbols.namesake ,D band ,Local density of states ,Valence (chemistry) ,Photoemission spectroscopy ,Computational chemistry ,Chemical physics ,Chemistry ,Fermi level ,symbols ,Density functional theory ,Nuclear magnetic resonance spectroscopy ,Quantum - Abstract
Publisher Summary This chapter demonstrates the electronic investigative power of electrochemical nuclear magnetic resonance spectroscopy (EC-NMR). The chapter correlates the two most important physical attributes—the Fermi level local density of states (Ef-LDOS) and the d band center—in defining the catalytic activity of a metal surface. Using CO adsorption as a paradigm, the unique and detailed electronic/mechanistic insights on the CO–metal bonding can be obtained. They are usually complimentary to those obtained from the other spectroscopic methods. Additionally, under certain qualitative assumptions presented in the chapter, some simple correlations between the trend of variations in the Ef-LDOS and the trend of variations in the d band center can be established. The former trend can in principle be obtained by EC-NMR while the latter by quantum density functional theory (DFT) calculations or by photoemission spectroscopy of valence bands and core levels. The consistency in reasoning and predictions obtained using both attributes has been excellent so far, thus ensuring a sound physical basis for such an approach. The complementary nature of these two attributes if correlated should enable the catalytic activity of a metal surface to be better and more comprehensively defined and understood. These correlations strengthen further the ability of EC-NMR in offering a detailed electronic picture of metal–adsorbate bonding interactions by extending its base of theoretical rationales.
- Published
- 2007