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Vibrational Stark shift spectroscopy of catalysts under the influence of electric fields at electrode-solution interfaces.

ABSTRACT: External control of chemical processes is a subject of widespread interest in chemical research, including control of electrocatalytic processes with significant promise in energy research. The electrochemical double-layer is the nanoscale region next to the electrode/electrolyte interface where chemical reactions typically occur. Understanding the effects of electric fields within the electrochemical double layer requires a combination of synthesis, electrochemistry, spectroscopy, and theory. In particular, vibrational sum frequency generation (VSFG) spectroscopy is a powerful technique to probe the response of molecular catalysts at the electrode interface under bias. Fundamental understanding can be obtained via synthetic tuning of the adsorbed molecular catalysts on the electrode surface and by combining experimental VSFG data with theoretical modelling of the Stark shift response. The resulting insights at the molecular level are particularly valuable for the development of new methodologies to control and characterize catalysts confined to electrode surfaces. This Perspective article is focused on how systematic modifications of molecules anchored to surfaces report information concerning the geometric, energetic, and electronic parameters of catalysts under bias attached to electrode surfaces.

SUBMITTER: Bhattacharyya D

PROVIDER: S-EPMC8336477 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Over the past decade, we have developed a spectroscopic approach to measure electric fields inside matter with high spatial (<1 Å) and field (<1 MV/cm) resolution. The approach hinges on exploiting a physical phenomenon known as the vibrational Stark effect (VSE), which ultimately provides a direct mapping between observed vibrational frequencies and electric fields. Therefore, the frequency of a vibrational probe encodes information about the local electric field in the vicinity around the probe. The VSE method has enabled us to understand in great detail the underlying physical nature of several important biomolecular phenomena, such as drug-receptor selectivity in tyrosine kinases, catalysis by the enzyme ketosteroid isomerase, and unidirectional electron transfer in the photosynthetic reaction center. Beyond these specific examples, the VSE has provided a conceptual foundation for how to model intermolecular (noncovalent) interactions in a quantitative, consistent, and general manner. The starting point for research in this area is to choose (or design) a vibrational probe to interrogate the particular system of interest. Vibrational probes are sometimes intrinsic to the system in question, but we have also devised ways to build them into the system (extrinsic probes), often with minimal perturbation. With modern instruments, vibrational frequencies can increasingly be recorded with very high spatial, temporal, and frequency resolution, affording electric field maps correspondingly resolved in space, time, and field magnitude. In this Account, we set out to explain the VSE in broad strokes to make its relevance accessible to chemists of all specialties. Our intention is not to provide an encyclopedic review of published work but rather to motivate the underlying framework of the methodology and to describe how we make and interpret the measurements. Using certain vibrational probes, benchmarked against computer models, it is possible to use the VSE to measure absolute electric fields in arbitrary environments. The VSE approach provides an organizing framework for thinking generally about intermolecular interactions in a quantitative way and may serve as a useful conceptual tool for molecular design.

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Vibrational Stark shift spectroscopy of catalysts under the influence of electric fields at electrode-solution interfaces.

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