Insituinfrared spectroelectrochemistry
作者:
Carol Korzeniewski,
Stanley Pons,
期刊:
Journal of Vacuum Science&Technology B: Microelectronics Processing and Phenomena
(AIP Available online 1985)
卷期:
Volume 3,
issue 5
页码: 1421-1424
ISSN:0734-211X
年代: 1985
DOI:10.1116/1.583002
出版商: American Vacuum Society
关键词: ELECTROCHEMISTRY;STARK EFFECT;INFRARED SPECTRA;FOURIER TRANSFORM SPECTROSCOPY;VIBRATIONAL STATES;ELECTRIC FIELD EFFECTS;DIPOLE MOMENTS;ABSORPTION SPECTRA;ABSORPTIVITY;ELECTRODES;GOLD;ADSORPTION;ACRYLONITRILE;PYRENE;SOLID−FLUID INTERFACES
数据来源: AIP
摘要:
The vibrational spectrum of molecules at or near an electrode surface can be obtained using subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) and electromodulated infrared spectroscopy (EMIRS). The large electric field existing at the electrode/solution interface is sufficient to induce dipole moments in highly polarizable molecules. The magnitude of the induced dipole moment is proportional to the electric field strength. As a result of this interaction some totally symmetric normal vibrations are made infrared active, and other bands appear in violation of the surface selection rule. This effect is known as the electrochemical Stark effect. Calculation of the expected absorption coefficients for the totally symmetric modes of adsorbed species gives values which are close to those observed experimentally. Experimental evidence ofAgmode activation of adsorbed pyrene is presented. The electric field dependence of the integrated absorption coefficient is demonstrated for acrylonitrile adsorbed on a gold electrode.
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