Investigating charge transfer dynamics at the nanoscale

TL;DR

This paper presents a novel quantitative approach using STM to study charge transfer dynamics at the nanoscale, focusing on a Nickel-tetraphenylporphyrin molecule on silicon, revealing specific pathways and energy levels involved.

Contribution

It introduces an original method combining statistical STM analysis and modeling to investigate charge transfer mechanisms at the single-molecule level.

Findings

Identified two optimal locations for molecular switching efficiency.

Demonstrated charge transfer propagates from aryl groups to the macrocycle.

Estimated key parameters of charge transfer dynamics using a Marcus-Jordner model.

Abstract

Acquiring quantitative information on charge transfer (CT) dynamics at the nanoscale remains an important scientific challenge. In particular, CT processes in single molecules at surfaces needs to be investigated to be properly controlled in various devices. To address this issue, the dynamics of switching molecules can be exploited. Here, a Nickel-tetraphenylporphyrin adsorbed on the Si(100) surface is used to study the CT process ruling the reversible activation of two chiral molecular conformations. Via the electrons of a scanning tunneling microscope (STM), a statistical study of the molecular switching reveals two specific locations of the molecule for which their efficiency is optimized. The CT mechanism is shown to propagate from two lateral aryls groups towards the porphyrin macrocycle inducing an intramolecular movement of two symmetric pyrroles. The measured switching efficiencies can thus be related with a Markus-Jordner model to estimate relevant parameters that describe the dynamics of the CT process. Numerical simulations provide a precise description of the molecular conformations and unveil the molecular energy levels that are involved in the CT process. This quantitative method opens a completely original approach to study CT at the nanoscale.