Tuning molecular thermal conductance through endgroup modification and halogen substitution

TL;DR

This study demonstrates how chemical modifications, such as endgroup changes and halogen substitutions, can effectively tune the phononic thermal conductance of single molecules, providing a pathway for controlling heat flow at the molecular level.

Contribution

The paper introduces a workflow combining ab initio molecular dynamics and machine learning to predict and analyze how specific chemical modifications influence molecular thermal conductance.

Findings

Bromine-terminated chains have the lowest thermal conductance.

Amine and methyl groups result in higher conductance.

Thermal conductance saturates beyond eight carbon atoms.

Abstract

We demonstrate tuning of the phononic thermal conductance in single molecules with carbon-chain backbones through modifications of terminal groups and halogen substitution of hydrogen atoms. Our simulations focus on intrinsic molecular properties, and we employ a workflow based on {\it ab initio} molecular dynamics, enabling the training and development of machine-learned interatomic potentials. These potentials are subsequently used in classical nonequilibrium molecular dynamics simulations to extract thermal conductance coefficients. Replacing terminal methyl groups with amine, sulfur, or halogen substituents leads to pronounced changes in thermal conductance: bromine-terminated chains exhibit the lowest conductance, whereas amine and methyl-terminated chains show the highest. Additionally, single-atom substitution of hydrogen by fluorine or other halogens along the alkane backbone significantly reduces thermal transport. Finally, our simulations of the length dependence of thermal conductance in alkane chains containing 3-12 carbon atoms reveal its saturation beyond eight carbon atoms. Together, our findings show that simple chemical modifications offer a versatile route to controlling phononic heat flow in single molecules.