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In the 1970s and 1980s spectroscopic probes of surfaces interfaced with vacuum were developed. They revealed adsorbate surface structure patterns and electronic and vibrational for the adsorbed molecules and even their structures. Some surface sensitive spectroscopies were applicable to electrochemical interfaces. When the electrode potential is changed the surface electron chemical potentialElectron chemical potential (μe) and Fermi energyFermi energy (Ef) change proportionally. In cases with robust charged surface and double layerDouble layer, emersed electrodesEmersed electrodesinterrogated with UPSUltraviolet Photoemission Spectroscopy (UPS)and XPSX-ray Photoemission Spectroscopy (XPS) demonstrated the proportionality. Understanding the electrochemical vibrational tuning rateElectrochemical Vibrational Tuning Rates (EVTR) (EVTR) of adsorbed molecules such as CO spurred the development of two theoretical viewpoints, one focusing on the electron chemical potential and valence electron band position of the electrode in the sense of Gurney and the other focusing on the presumed double layer electric field. Perturbation theory and semiempirical MO theory that could be applied to understand EVTR trends with the Gurney picture are outlined. Theories relating EVTR to bond lengths and force constants are reviewed. To provide an ability to calculate EVTRElectrochemical Vibrational Tuning Rates (EVTR) trends, a theory relating the vibrational force constants to bond lengths using electron density distribution functions in atoms is also outlined. Application of the electric fieldElectric field Stark effect as a model to explain EVTR is discussed.

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Interplay of New Spectroscopies and Semiempirical Quantum Theory Applied to Electrochemistry: 1970s–1980s. The Chemical Bond is Robust Under Perturbation

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  • 发表日期：

    2025年

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  • Alfred Anderson

摘要

In the 1970s and 1980s spectroscopic probes of surfaces interfaced with vacuum were developed. They revealed adsorbate surface structure patterns and electronic and vibrational for the adsorbed molecules and even their structures. Some surface sensitive spectroscopies were applicable to electrochemical interfaces. When the electrode potential is changed the surface electron chemical potentialElectron chemical potential (μe) and Fermi energyFermi energy (Ef) change proportionally. In cases with robust charged surface and double layerDouble layer, emersed electrodesEmersed electrodesinterrogated with UPSUltraviolet Photoemission Spectroscopy (UPS)and XPSX-ray Photoemission Spectroscopy (XPS) demonstrated the proportionality. Understanding the electrochemical vibrational tuning rateElectrochemical Vibrational Tuning Rates (EVTR) (EVTR) of adsorbed molecules such as CO spurred the development of two theoretical viewpoints, one focusing on the electron chemical potential and valence electron band position of the electrode in the sense of Gurney and the other focusing on the presumed double layer electric field. Perturbation theory and semiempirical MO theory that could be applied to understand EVTR trends with the Gurney picture are outlined. Theories relating EVTR to bond lengths and force constants are reviewed. To provide an ability to calculate EVTRElectrochemical Vibrational Tuning Rates (EVTR) trends, a theory relating the vibrational force constants to bond lengths using electron density distribution functions in atoms is also outlined. Application of the electric fieldElectric field Stark effect as a model to explain EVTR is discussed.