Modulation of Charge Transport through Single Molecules Induced by Solvent-Stabilized Intramolecular Charge Transfer

The modulation of charge transport through single molecules can be established by using the intrinsic characteristics of molecules and the physical properties of their environment. Therefore, the impact of the solvent on the electronic properties of molecules in the junction and their charge transport behavior are of great interest. Here, for the first time, we focused on charge transport through dimethylaminobenzonitrile (DMABN). This molecule shows unique behavior, specifically noticeable electronic structure modulations in bulk solvents, e.g., dual fluorescence in a polar environment. Using the scanning tunneling microscopy break junction (STM-BJ) technique, we find an order of magnitude increase in conductance along with a second conductance value in polar solvents over nonpolar solvents. Inspired by the twisted intramolecular charge transfer (TICT) explanation of the famous dual fluorescence of DMABN in polar solvents, we hypothesize stabilization of twisted DMABN molecules in the junction in more polar solvents. Ab initio molecular dynamics (AIMD) simulations using density functional theory (DFT) show that DMABN can twist in the junction and have a larger dipole moment compared to planar DMABN junction geometries, supporting the hypothesis. The nonequilibrium Green's function with the DFT approach (NEGF-DFT) is used to calculate the conductance throughout the AIMD trajectory, finding a significant change in the frontier orbitals and transmission function at large internal twisting angles, which can explain the dual conductance in polar solvents in STM-BJ experiments.