Tuning Molecular Thermal Conductance through End-Group Modification and Halogen Substitution

We demonstrate the tuning of 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 ab initio molecular dynamics, enabling the training and development of machine-learned interatomic potentials. These potentials are subsequently used in 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.