Orientational Effects and Molecular-Scale Thermoelectricity Control

The orientational effect concept in a molecular-scale junction is established for asymmetric junctions, which requires the fulfillment of two conditions: (1) design of an asymmetric molecule with strong distinct terminal end groups and (2) construction of a doubly asymmetric junction by placing an asymmetric molecule in an asymmetric junction to form a multicomponent system such as Au/Zn-TPP+M/Au. Here, we demonstrate that molecular-scale junctions that satisfy the conditions of these effects can manifest Seebeck coefficients whose sign fluctuates depending on the orientation of the molecule within the asymmetric junction in a complete theoretical investigation. Three anthracene-based compounds are investigated in three different scenarios, one of which displays a bithermoelectric behavior due to the presence of strong anchor groups, including pyridyl and thioacetate. This bithermoelectricity demonstration implies that if molecules with alternating orientations can be placed between an asymmetric source and drain, they can be potentially utilized for increasing the thermovoltage in molecular-scale thermoelectric energy generators (TEGs).