Infrared spectrum of carbon monoxide on a platinum electrode in acidic solution

Russell, Joel W.; Overend, John; Scanlon, Kerin; Severson, Mark W.; Bewick, A.

doi:10.1021/j100213a005

Cited by 119 publications

(29 citation statements)

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“…Russel et al for the first time applied PM IRRAS to the electrochemical interface [74]. At the IR mirror surface the electric field of the s-polarized IR light is equal to zero, thus the absorption of the s-polarized light contains spectral information from the environment surrounding the sample (a background spectrum).…”

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

“…By contrast, the electric field of the p-polarized light is enhanced at the mirror surface. Therefore, adsorbed molecules can absorb the light if the transition dipole vector of a vibrational transition has a non-zero component normal to the surface of the mirror [45,74]. Due to the modulation of the light polarization the background and sample spectra are collected simultaneously.…”

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

“…In polarization modulation infrared reflection absorption spectroscopy (PM IR-RAS) an incident IR beam is modulated between the s-and p-polarization and thus the resulting reflection-absorption spectrum of species adsorbed on the metal|air interface is almost insensitive to the absorption of water vapour and CO 2 from the atmosphere [45,51,74,81]. Russel et al for the first time applied PM IRRAS to the electrochemical interface [74].…”

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

“…Due to constructional problems of the cell and adjustment of optical components before each experiment, a measurement of the reference spectrum from the electrolyte solution and the film adsorbed at the interface at exactly the same experimental conditions is not possible. Therefore, the background correction is done either by a potential [18,[70][71][72][73] or polarization modulation of the incident radiation [45,64,74]. When potential is modulated and IRRA spectra collected using p-polarized light the experimental techniques are called subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) or potential modulated infrared reflectance spectroscopy.…”

Section: Irras Techniques Used In Electrochemcial Experimentsmentioning

confidence: 99%

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Application of Polarization Modulation Infrared Reflection Absorption Spectrosocpy Under Electrochemical Control for Structural Studies of Biomimetic Assemblies

Brand

2015

Zeitschrift Für Physikalische Chemie

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An ideal bioanalytical method would allow carrying out sensitive, selective, reproducible, fast, and in situ chemical measurements of the composition, structure and function of complex biological systems. Physical chemistry possesses advanced structure analyzing techniques which are suitable to solve, at a sub-molecular level, the structure of biomolecules. However, the prerequisite of the presence of the electrolyte solution limits the number of applicable structure analyzing techniques. Infrared spectroscopy is one of the most powerful analytical techniques used to identify the structure of biomolecules, monitor structural changes under various experimental environments and physical states. In addition, infrared reflection absorption spectroscopy (IRRAS) has been successfully applied to study supramolecular films at the solid|liquid interface. Assemblies of biomolecules belong to a particularly demanding because they bring specific for the maintenance of their functions experimental requirements which have to be taken into account planning in situ spectroelectrochemical experiments. In this paper potnential of in situ IRRAS under electrochemical control for studies of structural changes in assemblies of biomolecules such as lipid bilayers and protein films is described. Studies of different classes of biomolecules bring certain experimetnal conditions concerning the electrolyte composition, pH value, temperature or chemical nature of the solid support, which have to be fulfilled. Obviously, these conditons may significantly restrict the applicability of the in situ PM IRRAS. The selection of the solid substrate with required optical and electrical properties, the optical window and the electrolyte composition have to be adapted to the needs of biomolecules. Adjustement of experimetnal conditions as well as possibilites of the enlargement of the in situ PM IRRAS for studies of biomimetic assemblies is reviewed in this paper. Furthermore, experimetnal resutls reporting potenial driven changes in models of cell membranes and protein films are reviewed. Pioneering studies aiminig at the determination of structural changes in lipid membranes exposed to physiological electric fields and interacting simultaneously with protiens are described.

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Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

Section: Polarization Modulation Infrared Reflection Absorption Spectmentioning

confidence: 99%

Section: Irras Techniques Used In Electrochemcial Experimentsmentioning

confidence: 99%

See 2 more Smart Citations

Application of Polarization Modulation Infrared Reflection Absorption Spectrosocpy Under Electrochemical Control for Structural Studies of Biomimetic Assemblies

Brand

2015

Zeitschrift Für Physikalische Chemie

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“…The major advantage is that spectra are obtained at a constant potential. This allows the unambiguous interpretation of parameters such as peak frequency, or a shift in peak frequency, both of which are not unambiguously determinable using EMIRS (26,27). Since the resulting spectrum in EMIRS often has a bisignate shape (resembling the differential of an absorption band), a large number of original spectra can account for the resulting spectrum.…”

Section: Electrochemical Methodsmentioning

confidence: 99%

Laser-induced thermal decay of pyridine and chloride. Surface-enhanced Raman scattering as a probe of silver surface-active sites

Sobocinski

Pemberton²

1988

Langmuir

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The activation parameters for the temperature-dependent irreversible loss of surface-enhanced Raman scattered (SERS) intensity from pyridine and chloride adsorbed at silver surfaces in an electrochemical environment have been determined. Laser-induced heating is used to promote a first-order surface reaction at these roughened silver electrodes and is introduced as a probe of the chemical nature of SERS-active sites. Accurate laser-induced surface temperatures must be known for these experiments and are calculated from spectroscopic data. It is found that the kinetic data follow Arrhenius behavior for both pyridine and chloride. The activation energies associated with the destruction of SERS-active sites at a surface roughened by an illuminated oxidation-reduction cycle (ORC) are 12.8 ± 3.2 and 27.7 ± 3.1 kcal/mol for pyridine at two different types of sites on the Ag surface. Similarly, values for coadsorbed chloride are found to be 11.1 ± 2.4 and 24.5 ± 3.8 kcal/mol. Experiments designed to elucidate the decay mechanism suggest that the laser-induced surface reaction involves desorption of pyridine and chloride from active sites allowing their incorporation into the Ag lattice. The observation of two activation energies in the same temperature region is interpreted in terms of SERS-active sites, which exist at a surface defect and on a terrace plane, respectively. This interpretation is based on the relative activation energies and preexponential factors. The activation parameters for pyridine and chloride desorption are also evaluated at a silver surface roughened by a nonilluminated ORC. An activation energy of 27.4 ± 1.9 kcal/mol is obtained for pyridine on these surfaces. This result suggests that a greater concentration of terrace plane SERS-active sites is present at a surface roughened by an illuminated ORC.

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Infrared Spectroelectrochemistry

Korzeniewski

2001

Handbook of Vibrational Spectroscopy

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The sections in this article are Introduction Experimental Infrared Spectrometer Systems Sampling Methods External Reflection Attenuated Total Internal Reflection Thin‐Layer Electrochemical Cells for in situ Infrared Measurements Spectral Acquisition Electrochemically Modulated Infrared and Subtractive Fourier Transform Infrared Spectroscopic Methods Double‐Modulation Fourier Transform Infrared Spectroscopic Methods Polarization Modulation Electrode Potential Modulation Applications Electrocatalysis and CO Surface Chemistry Adsorbed CO : Surface Coverage Effects Infrared Spectroscopy of in situ Scanning Tunneling Microscopy‐Characterized Metal–Adsorbate Systems Adsorbed CO : Surface Potential Effects Discrimination Against Solution Species with Fourier Transform Electrochemically Modulated Infrared Spectroscopy Organic Monolayers Summary and Conclusions Acknowledgments

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Infrared spectrum of carbon monoxide on a platinum electrode in acidic solution

Abstract: If Wegner's model is correct, then the /3-carotene results suggest that stacks of conjugated segments of (CH), occur in the absence of chain folding and, after doping, are involved in charge transfer perpendicular to the segment axes.

Cited by 119 publications

References 0 publications

Application of Polarization Modulation Infrared Reflection Absorption Spectrosocpy Under Electrochemical Control for Structural Studies of Biomimetic Assemblies

Application of Polarization Modulation Infrared Reflection Absorption Spectrosocpy Under Electrochemical Control for Structural Studies of Biomimetic Assemblies

Laser-induced thermal decay of pyridine and chloride. Surface-enhanced Raman scattering as a probe of silver surface-active sites

Infrared Spectroelectrochemistry

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