fulltext.study @t Gmail

Thermodynamic analysis of some electrochemical properties of transition metal complexes in electronically excited states

Paper ID Volume ID Publish Year Pages File Format Full-Text
28232 44066 2007 8 PDF Available
Title
Thermodynamic analysis of some electrochemical properties of transition metal complexes in electronically excited states
Abstract

A theoretical treatment is presented of the relationship between absorption and emission maxima for (0–0) electronic transitions in transition metal complexes such as the ruthenium(II) polypyridyl chromophores used as dye sensitizers in photovoltaic cells, and the corresponding shift in standard redox (or half-wave) potential of these ionic complexes. It is shown that the potential shift is proportional to the average of absorption and emission wavenumbers for oxidized or reduced forms, a result that follows from a detailed analysis of medium relaxation effects, based on the Onsager cavity model, and attendant solvatochromic shifts. It is also shown how additional thermodynamic properties (reaction entropies and enthalpies) pertaining to the half reaction if the reactants are present in solution can be obtained from observation of the variation of spectra with temperature.For the case of reactants present in an insoluble monolayer, a general expression is derived for the Gibbs energy change that results from the promotion of all absorbing species to an excited state, and the changes in Gibbs energy resulting from the processes that return the system to ground-state equilibrium.

Keywords
Photoelectrochemistry; Photovoltaics; Standard redox potential; Thermodynamic cycle; Franck–Condon principle; Onsager cavity model; Solvatochromic shifts; Reaction entropy; Reaction enthalpy; Monolayer
First Page Preview
Thermodynamic analysis of some electrochemical properties of transition metal complexes in electronically excited states
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us
Publisher
Database: Elsevier - ScienceDirect
Journal: Journal of Photochemistry and Photobiology A: Chemistry - Volume 187, Issues 2–3, 15 April 2007, Pages 247–254
Authors
,
Subjects
Physical Sciences and Engineering Chemical Engineering Bioengineering
Get Full-Text Now
Don't Miss Today's Special Offer
Price was $35.95
You save - $31
Price after discount Only $4.95
100% Money Back Guarantee
Full-text PDF Download
Online Support
Any Questions? feel free to contact us