Quantum Rate Electrodynamics and Resonant Junction Electronics of Heterocyclic Molecules

TL;DR

This paper demonstrates that charge transfer in heterocyclic molecular junctions follows relativistic quantum mechanics and quantum rate theory, revealing fundamental electrodynamic principles governing electron transfer in these systems.

Contribution

It introduces a quantum rate electrodynamics framework for heterocyclic molecules, linking molecular charge transfer to relativistic quantum mechanics and resonant quantum conductance.

Findings

Charge transfer frequencies follow the quantum rate theory prediction.

Differences in molecular junctions are due to adiabatic quantum conductance settings.

Electrolyte environment influences resonant quantum conductance dynamics.

Abstract

Quantum rate theory encompasses the electron-transfer rate constant concept of electrochemical reactions as a particular setting, besides demonstrating that the electrodynamics of these reactions obey relativistic quantum mechanical rules. The theory predicts a frequency $\nu = E/h$ for electron-transfer reactions, in which $E = e^2/C_q$ is the energy associated with the density-of-states $C_q/e^2$ and $C_q$ is the quantum capacitance of the electrochemical junctions. This work demonstrates that the $\nu = E/h$ frequency of the intermolecular charge transfer of push-pull heterocyclic compounds, assembled over conducting electrodes, follows the above-stated quantum rate electrodynamic principles. Astonishingly, the differences between the molecular junction electronics formed by push-pull molecules and the electrodynamics of electrochemical reactions observed in redox-active modified electrodes are solely owing to an adiabatic setting (strictly following Landauer's ballistic presumption) of the quantum conductance in the push-pull molecular junctions. An appropriate electrolyte field-effect screening environment accounts for the resonant quantum conductance dynamics of the molecule-bridge-electrode structure, in which the intermolecular charge transfer dynamics within the frontier molecular orbital of push-pull heterocyclic molecules follow relativistic quantum mechanics in agreement with the quantum rate theory.