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Kinetic Isotope Effect on Electron Transfer Rates Across Self-Assembled Monolayers: A Case for Quantum Effects

preprint
submitted on 04.10.2019 and posted on 07.10.2019 by Samir Chattopadhyay, Sabyasanchi Bandyopadhyay, Abhishek Dey
Long range ET across several self-assembled mon-olayer (SAM) covered Au electrodes is investigated using protonated and deuterated thiols (RSH/RSD). The rate of tunneling is measured using both chronoamperometry and cyclic voltammetry and it shows a prominent KIE. The KIE is ~2 (normal) for medium chain length thiols where the Tafel plot indicate substantial through space tunneling and is ~0.25 (inverse) for long chain thiols where the Tafel plot indicate mostly through bond tunneling. These results imply substantial contribution from the classical modes at the Au-(H)SR interface, which shift substantially on deuteration of the thiols, to the ET process.

Funding

Department of Science and Technology, SERB, India

History

Email Address of Submitting Author

icad@iacs.res.in

Institution

Indian Association for the Cultivation of Science

Country

India

ORCID For Submitting Author

0000-0002-9166-3349

Declaration of Conflict of Interest

None

Version Notes

this is the first version

Exports