Quantum rate electrodynamics and resonant junction electronics of heterocyclic molecules

Author(s)

Nieto, Edgar Fabian Pinzon ; Lopes, Lais Cristine ; dos Santos, Adriano ; Raposo, Maria Manuela Marques ; Bueno, Paulo Roberto

• Document type: Journal article
• Source: Electrochimica Acta; v. 501, p. 12-pg., 2024-08-02.

Abstract

The quantum rate theory provides a framework to understand electron-transfer reactions by correlating the electron-transfer rate constant (v) v ) with the quantum capacitance (Cq) C q ) and the molecular conductance (G). G ). This theory, which is rooted in relativistic quantum electrodynamics, predicts a fundamental frequency v = 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. (AU)

• FAPESP's process: 17/24839-0 - Nanoelectronics and nanoscale electrochemistry: fundaments and applications
• Grantee: Paulo Roberto Bueno
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 18/24525-9 - Nanoelectronics and nanoscale electrochemistry: fundaments and applications
• Grantee: Edgar Fabian Pinzon Nieto
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)