Quantum rate electrodynamics and resonant junction electronics of heterocyclic molecules

• Autor(es): Pinzón Nieto, Edgar Fabian ; Lopes, Laís Cristine ; Santos, Adriano dos ; Raposo, M. Manuela M. ; Bueno, Paulo Roberto
• Data: 2024
• Identificador Persistente: https://hdl.handle.net/1822/90778
• Origem: RepositóriUM - Universidade do Minho
• Tipo de Documento: Artigo científico
• Idioma: Inglês
• Contribuidor(es): Universidade do Minho

Descrição

The quantum rate theory provides a framework to understand electron-transfer reactions by correlating the electron-transfer rate constant () with the quantum capacitance () and the molecular conductance (). This theory, which is rooted in relativistic quantum electrodynamics, predicts a fundamental frequency = ∕ℎ for electron-transfer reactions, where is the energy associated with the density of states ∕2. This work demonstrates the applicability of the quantum rate theory to the intermolecular charge transfer of push-pull heterocyclic compounds assembled over conducting electrodes. Remarkably, the observed differences between molecular junction electronics formed by push-pull molecules and the electrodynamics of electrochemical reactions on redox-active modified electrodes can be attributed solely to the adiabatic setting of the quantum conductance in push-pull molecular junctions. The electrolyte field-effect screening environment plays a crucial role in modulating the resonant quantum conductance dynamics of the molecule-bridge-electrode structure. In this context, the intermolecular electrodynamics within the frontier molecular orbital of push-pull heterocyclic molecules adhere to relativistic quantum mechanics, consistent with the predictions of the quantum rate theory

The quantum rate theory provides a framework to understand electron-transfer reactions by correlating the electron-transfer rate constant ($\nu$) with the quantum capacitance ($C_q$) and the molecular conductance ($G$). This theory, which is rooted in relativistic quantum electrodynamics, predicts a fundamental frequency $\nu = E/h$ for electron-transfer reactions, where $E$ is the energy associated with the density of states $C_q/e^2$. This work demonstrates the applicability of the quantum rate theory to the intermolecular charge transfer of push-pull heterocyclic compounds assembled over conducting electrodes. Remarkably, the observed differences between molecular junction electronics formed by push-pull molecules and the electrodynamics of electrochemical reactions on redox-active modified electrodes can be attributed solely to the adiabatic setting of the quantum conductance in push-pull molecular junctions. The electrolyte field-effect screening environment plays a crucial role in modulating the resonant quantum conductance dynamics of the molecule-bridge-electrode structure. In this context, the intermolecular electrodynamics within the frontier molecular orbital of push-pull heterocyclic molecules adhere to relativistic quantum mechanics, consistent with the predictions of the quantum rate theory.