Kinetics Of Electron Transfer Processes Research Articles

Driving chemical reactions with polariton condensates

When molecular transitions strongly couple to photon modes, they form hybrid light-matter modes called polaritons. Collective vibrational strong coupling is a promising avenue for control of chemistry, but this can be deterred by the large number of quasi-degenerate dark modes. The macroscopic occupation of a single polariton mode by excitations, as observed in Bose-Einstein condensation, offers promise for overcoming this issue. Here we theoretically investigate the effect of vibrational polariton condensation on the kinetics of electron transfer processes. Compared with excitation with infrared laser sources, the vibrational polariton condensate changes the reaction yield significantly at room temperature due to additional channels with reduced activation barriers resulting from the large accumulation of energy in the lower polariton, and the many modes available for energy redistribution during the reaction. Our results offer tantalizing opportunities to use condensates for driving chemical reactions, kinetically bypassing usual constraints of fast intramolecular vibrational redistribution in condensed phase.

Study of effectiveness of pyrene concentration dependence on the kinetics of electron transfer process with N,N-dimethylaniline in condensed phase

The role of another excited pyrene molecule in the vicinity of an excited pyrene molecule undergoing electron transfer (ET) process with a N,N,-dimethylaniline molecule has been explored in non-polar and polar solvents where specifically solvent mediated nature of ET is prominent. Analytic expression has been derived for the dependence of ET kinetics on pyrene concentration in the experimental conditions normally encountered in sub-nanosecond time correlated single photon counting (TCSPC) apparatus which is mostly used. The life time data has been explained on the basis of present day understanding.

Investigation of the kinetics of electron transfer processes involving fullerenes at liquid–liquid interfaces using scanning electrochemical microscopy: evidence for Marcus inverted region behaviour

Download options Please wait... Article information DOI https://doi.org/10.1039/B102734B Article type Paper Submitted 26 Mar 2001 Accepted 18 Jun 2001 First published 18 Jul 2001 Download Citation J. Chem. Soc., Perkin Trans. 2, 2001, 1608-1612 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Investigation of the kinetics of electron transfer processes involving fullerenes at liquid–liquid interfaces using scanning electrochemical microscopy: evidence for Marcus inverted region behaviour J. Zhang and P. R. Unwin, J. Chem. Soc., Perkin Trans. 2, 2001, 1608 DOI: 10.1039/B102734B To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Search articles by author Jie Zhang Patrick R. Unwin

Synthesis and Structure of a Dimeric Peralkylated Hexaaminobenzene: Hexakis(dimethylamino)hexamethyl‐hexaaza[63] (1,3,5)cyclophane

Increasing the reorganization energy slows intramolecular electron transfer (ET) in 1, a compound thus well-suited for studying the kinetics of ET processes. A surprisingly smooth, threefold nucleophilic aromatic substitution reaction is the key step in the synthesis of 1.

Kinetics of electron transfer processes involving free ions and ion pairs studied by flash photolysis

Photoejection of electrons from pyrenide ions (π. - ) or sodium pyrenide ion pairs (π. - , Na + ) was effected in tetrahydrofuran (THF) or tetrahydropyran (THP) solution by flash of light (λ > 420 nm). As the reaction was performed in the presence of a large excess of biphenyl (B) the ejected electrons were captured preferentially by that hydrocarbon reducing it to biphenylide radical ion (B. - or B. - , Na + ). Due to the low concentration of pyrene (π) the subsequent reactions between biphenylide and pyrene, namely B. - + π ( k 1 →) B + π. - (1) and B. - , Na + + π ( k 2 →) B + π. - , Na + , (2) could be easily monitored after the flash. By varying the ratio of [B. - ]/[B. - , Na + ] it was possible to make either (1) or (2) dominant, and hence to determine the rate constants k 1 and k 2 . Thus, k 1 = (4.8 ± 0.5) x 10 10 1 mol -1 s -1 and k 2 = 0.6 x 10 10 1 mol -1 s -1 for the electron transfer in THF, and k 2 = 0.5 x 10 10 1 mol -1 s -1 for the reaction in THP, all the constants referring to ≈ 20 °C.

Electron Transfer and Thermal Racemization of Ethylenediaminetetraacetato-cobaltate(III)

IN general, electron-transfer reactions which involve no net chemical change have been studied by the use of isotopic tracers. In 1950, Dwyer and Gyarfas1 reported that the mixing of d-tris(2,2′-bipyridine)-osmium(II) with 1-tris(2,2′-bipyridine)osmium(III) was followed by the very rapid loss of all optical activity. This was explained by assuming that a rapid electron transfer process led to redistribution of the dextro and laevo configurations among the two oxidation states. Consequently, Dwyer and Gyarfas suggested that optical activity should provide a second convenient method for the study of the kinetics of electron-transfer processes.