Theoretical and experimental methods for in situ infrared spectroelectrochemistry of organic monomolecular films

Thesis/Dissertation · Wed Sep 09 04:00:00 EDT 1992

OSTI ID:10184740

Popenoe, D D

This work describes the theoretical analysis, experimental development, and application of an in situ spectroelectrochemical cell for measuring infrared reflection-absorption spectra (IRRAS) of monolayer-coated Au surfaces beneath a thin aqueous overlayer. The cell allows the interchange of sample and reference substrates, thereby facilitating IRRAS of long-chain alkanethiolates in the C-H stretching region without electrochemical or polarization-modulation methods. The same in situ cell is combined with electrochemical modulation to study monolayers self-assembled from 11-mercaptoundecyl ferrocenecarboxylate (FcCOOC{sub 11}SH) at gold and to correlate the monolayer structure and composition with the ferrocenyl redox chemistry. An electrochemically active monolayer of an alkanethiolate derivatized with a flavin, formed by self-assembly from ethanolic solutions of 11,11`-dithiobisundecanoic acid, bis[2-(7,8-dimethyl-10-isoalloxazino)ethyl] ester, is described. IRRAS of the film, which is a candidate for future in situ spectroscopic studies, are presented and compared with transmission spectra of bulk analogs.

• Research Organization: Ames Lab., IA (United States)
• Sponsoring Organization: USDOE, Washington, DC (United States)
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 10184740
• Report Number(s): IS-T--1607; ON: DE93001222
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201
ABSORPTION SPECTRA
CHEMICAL AND PHYSICOCHEMICAL PROPERTIES
ELECTROCHEMICAL CELLS
FERROCENE
GOLD
INFRARED SPECTRA
IRON COMPLEXES
ISOALLOXAZINES
LAYERS
MOLECULES
REFLECTION
SPECTRAL REFLECTANCE
SURFACE COATING
SURFACES
VIBRATIONAL STATES