Probing electronic excitations in molecular conduction

TL;DR

This paper investigates how electronic excitations influence the current-voltage characteristics in molecular conduction, revealing experimental signatures linked to many-electron spectrum features using a multielectron approach.

Contribution

It introduces a multielectron master equation method to analyze I-V characteristics, capturing complex excitation effects beyond standard one-electron theories.

Findings

Identifies experimental signatures of many-electron excitations in I-V curves

Explains nontrivial features in I-V characteristics with a multielectron model

Highlights limitations of one-electron SCF theories in molecular conduction

Abstract

We identify experimental signatures in the current-voltage (I-V) characteristics of weakly contacted molecules directly arising from excitations in their many electron spectrum. The current is calculated using a multielectron master equation in the Fock space of an exact diagonalized model many-body Hamiltonian for a prototypical molecule. Using this approach, we explain several nontrivial features in frequently observed I-Vs in terms of a rich spectrum of excitations that may be hard to describe adequately with standard one-electron self-consistent field (SCF) theories.