First-principles calculation of the thermoelectric figure of merit for [2,2]paracyclophane-based single-molecule junctions

TL;DR

This study uses first-principles calculations to analyze thermoelectric transport in paracyclophane-based single-molecule junctions, highlighting the impact of chemical functionalization and phononic contributions on the thermoelectric figure of merit.

Contribution

It combines DFT and NEGF techniques with self-energy corrections to accurately predict thermoelectric properties, emphasizing the role of phonons and chemical tuning.

Findings

Functional groups mainly influence thermopower, allowing sign and magnitude tuning.

Functionalization can significantly enhance the electronic contribution to ZT.

Phononic thermal conductance strongly suppresses the overall ZT.

Abstract

Here we present a theoretical study of the thermoelectric transport through {[}2,2{]}para\-cyclo\-phane-based single-molecule junctions. Combining electronic and vibrational structures, obtained from density functional theory (DFT), with nonequilibrium Green's function techniques, allows us to treat both electronic and phononic transport properties at a first-principles level. For the electronic part, we include an approximate self-energy correction, based on the DFT+$\Sigma$ approach. This enables us to make a reliable prediction of all linear response transport coefficients entering the thermoelectric figure of merit $ZT$. Paracyclophane derivatives offer a great flexibility in tuning their chemical properties by attaching different functional groups. We show that, for the specific molecule, the functional groups mainly influence the thermopower, allowing to tune its sign and absolute value. We predict that the functionalization of the bare paracyclophane leads to a largely enhanced electronic contribution $Z_{\mathrm{el}}T$ to the figure of merit. Nevertheless, the high phononic contribution to the thermal conductance strongly suppresses $ZT$. Our work demonstrates the importance to include the phonon thermal conductance for any realistic estimate of the $ZT$ for off-resonant molecular transport junctions. In addition, it shows the possibility of a chemical tuning of the thermoelectric properties for a series of available molecules, leading to equally performing hole- and electron-conducting junctions based on the same molecular framework.