Nonadiabatic to Adiabatic Transition of Electron Transfer in Colloidal Quantum Dot Molecules

TL;DR

This study demonstrates how the electron transfer regime in colloidal quantum dot molecules can be tuned from nonadiabatic to adiabatic by adjusting physical parameters, revealing significant rate enhancements and mode couplings.

Contribution

It introduces a method to control electron transfer regimes in quantum dot molecules through structural tuning without changing reorganization energy or phonon frequency.

Findings

Electron transfer rates increase by orders of magnitude in the adiabatic limit.

Hybridization energy can be tuned by changing neck dimensions and quantum dot size.

Strong coupling of specific vibrational modes to charge transfer was identified.

Abstract

Electron transfer is an important and fundamental process in chemistry, biology and physics, and has received significant attention in recent years. Perhaps one of the most intriguing questions concerns with the realization of the transitions between nonadiabatic and adiabatic regimes of electron transfer, as the coupling (hybridization) energy, $J$, between the donor and acceptor is varied. Here, using colloidal quantum dot molecules, a new class of coupled quantum dot dimers, we computationally demonstrate how the hybridization energy between the donor and acceptor quantum dots can be tuned by simply changing the neck dimensions and/or the quantum dot size. This provides a handle to tune the electron transfer from the nonadiabatic over-damped Marcus regime to the coherent adiabatic regime in a single system, without changing the reorganization energy, $\lambda$, or the typical phonon frequency, $\omega_c$. We develop an atomistic model to account for several donor and acceptor states and how they couple to the lattice vibrations, and utilize the Ehrenfest mean-field mixed quantum-classical method to describe the charge transfer dynamics as the nonadiabatic parameter, $\gamma$, is varied. We find that charge transfer rates increase by several orders of magnitude as the system is driven to the coherent, adiabatic limit, even at elevated temperatures, and delineate the inter-dot and torsional acoustic modes that couple most strongly to the charge transfer reaction coordinate.