Reorganization energy from charge transport measurements in a monolithically$-$integrated molecular device
Abstract
Intermolecular charge transfer reactions are key processes in physical chemistry. The electron-transfer rates depend on a few system's parameters, such as temperature, electromagnetic field, distance between adsorbates and, especially, the molecular reorganization energy. This microscopic greatness is the energetic cost to rearrange each singlemolecule and its surrounding environment when a charge is transferred. Reorganization energies are measured by electrochemistry and spectroscopy techniques as well as at the single-molecule limit using atomic force microscopy approaches, but not from temperaturedependent charge transport measurements nor in a monolithicallyintegrated molecular device. Nowadays selfrolling nanomembrane (rNM) devices, with strainengineered mechanical properties, onachip monolithic integration, and operable in distinct environments, overcome those challenges. Here, we investigate the charge transfer reactions occurring within a ca. 6 nm thick copperphthalocyanine (CuPc) film employed as electrode-spacer in a monolithically integrated nanocapacitor. Employing the rNM technology allows us to measure the molecules' chargetransport dependence on temperature for different electric fields. Thereby, the CuPc reorganization energy is determined as (930 40) meV, whereas density functional theory (DFT) calculations support our findings with the atomistic picture of the CuPc charge transfer reaction. Our approach presents a consistent route towards electron transfer reaction characterization using currentvoltage spectroscopy and provides insight into the role of the molecular reorganization energy when it comes to electrochemical nanodevices.
Keywords
Cite
@article{arxiv.2312.02321,
title = {Reorganization energy from charge transport measurements in a monolithically$-$integrated molecular device},
author = {Leandro Merces and Graziâni Candiotto and Letícia M. M. Ferro and Anerise de Barros and Carlos V. S. Batista and Ali Nawaz and Antonio Riul and Rodrigo B. Capaz and Carlos C. Bof Bufon},
journal= {arXiv preprint arXiv:2312.02321},
year = {2023}
}
Comments
17 pages, 5 figures