Simon Pascal | Search arXiv

arXiv2026

Benzo-bis(imidazole) self-assembled monolayers molecular junctions in meta or para conformation: effects of protonation on the electrical and thermal conductances

We report the thermal conductances of molecular junctions made of self-assembled monolayers of benzo-bis(imidazole) molecules, without side groups or functionalized with two phenylamine side groups. In the two cases, when the molecules are connected to the electrodes by thiol anchoring groups in the meta-position, the thermal conductance is decreased compared to the same molecules connected in the para-position (ca. 16-29 nW/K and ca. 37-40 nW/K, respectively) in agreement with the theoretically predicted phonon interference effect in molecular junctions. Upon protonation, the thermal conductances of the meta-connected molecular junction increase by about 50% (reversible behavior upon deprotonation). The fact that only the thermal conductance of the meta-connected molecular junction is sensitive to the protonation/deprotonation is tentatively related to modifications of the structural organization of the molecules in the monolayer, which modifies the thermal conductance at the molecule/electrode interfaces. The electrical conductance is lower for the meta-connected molecule than for the para-connected one, due to destructive quantum interferences, as expected and reported for other molecular junctions. The conductance further decreases (reversibly) upon protonation. The energy position of the molecular orbital involved in the electron transport is not modified by the protonation and the decrease in current is related to changes in the molecule organization in the monolayer, which modulate the electronic coupling energy at the molecule/electrode interfaces.

cond-mat.mes-hall↗

arXiv2020

Significance of nuclear quantum effects in hydrogen bonded molecular chains

In hydrogen bonded systems, nuclear quantum effects such as zero-point motion and tunneling can significantly affect their material properties through underlying physical and chemical processes. Presently, direct observation of the influence of nuclear quantum effects on the strength of hydrogen bonds with resulting structural and electronic implications remains elusive, leaving opportunities for deeper understanding to harness their fascinating properties. We studied hydrogen-bonded one-dimensional quinonediimine molecular networks which may adopt two isomeric electronic configurations via proton transfer. Herein, we demonstrate that concerted proton transfer promotes a delocalization of {\pi}-electrons along the molecular chain, which enhances the cohesive energy between molecular units, increasing the mechanical stability of the chain and giving rise to new electronic in-gap states localized at the ends. These findings demonstrate the identification of a new class of isomeric hydrogen bonded molecular systems where nuclear quantum effects play a dominant role in establishing their chemical and physical properties. We anticipate that this work will open new research directions towards the control of mechanical and electronic properties of low-dimensional molecular materials via concerted proton tunneling.

cond-mat.mes-hall↗