Discovery of a coherent exchange of multiple electrons within the Au-deposited, self-assembled bio-derived hybrid quasi-2D nano-layers

Author: Dimitri Khoshtariya
Co-authors: Tinatin D. Dolidze, Nikoloz Nioradze, Mikhael Shushanyan, Tornike Kimeridze, Lasha Laliashvili, Maya Makharadze, Rudi van Eldik
Keywords: Gold deposited self-assembled nano-systems, Hybrid layers composed of L-cysteines and copper ions, Coherent transfers of multiple electrons, Ultra-narrow voltammetric curves, Spin-implicated exchanges, Boson condensation
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We report on the first direct voltammetric observation of a spectacular switch from the easily recognizable single electron exchange pattern, to the multi-electron (up to 10 electrons and more per single elementary act) mechanism, detected through the unprecedented, essentially two-state and fully substituted transformation of the normally-shaped cyclic voltammetry (CV) signal to the “atypical”, extremely sharply-peaked CV response, Figure 1, (a). This interplay has been observed for the Au-deposited L-cys self-assembled monolayer films (SAMs) nearly saturated by SAM-coordinated, fully redox-active Cu2+ ions, capable of acting either as individual redox-probes (as depicted before) [1] or, as multi-electron-carrier, collectively redox-active quasi-1D clusters, [(L-cysCO2)2Cu2+]n (where: n = 2, 4, ...10 ...), presumably ordered together through the spin-implicated Boson condensation [2,3] (this work). Careful cross-analysis, based on the combination of complementary rate theories, was applied to explain additional experimental details including effects of temperature and scan-rate variations, by considering direct dynamic control and nonergodic/nonlinear motifs for electronic transport, attributable to the glass-forming (protein-like) interfacial environments [1]. These 2D assemblies displaying unique voltammetric features potentially could be of considerable interest as a novel type of memory storage devices [3]. References [1] D. E. Khoshtariya et al., J. Phys. D, Appl. Phys. 48 (2015) 255402; [2] J. P. Eisenstein, Ann. Rev. Cond. Matt. Phys., 5 (2014) 159–181; [3] F. Hellman et al., Rev. Mod. Phys. 89 (2017) 025006.

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