Theory of quantum interference in molecular junctions

In recent years, electron transport through single molecules has attracted huge attention, since the molecules are promising building blocks for the next generation of electronic devices. To create molecular junctions and probe their electrical properties, intense experimental efforts and theoretical studies are underway. For single molecule electronic applications, an important property is their electrical conductance. In this context, I start my thesis by introducing a general discussion about some basic topics related to single molecule transport theory. Quantum interference effects have recently attracted great interest in studies of the charge transport at the single molecule scale. Within this framework, I study the single molecule conductances of five-membered ring compounds to investigate the effect of molecular symmetry and quantum interference on the charge transport through single molecule junctions. This theoretical and experimental study highlights the presence of destructive quantum interference and more importantly reveals that the control of molecular asymmetry via the heteroatom substitution allows the tuning of destructive quantum interference. Theoretically, I identify similar features over some range of energies using different anchoring groups and elucidate the impact of the anchoring groups on the charge transport through single molecule. Moreover, I find that molecular symmetry has a slight effect on the binding energies of the 1-8 compounds seen in Figure 3.1. Within the phase coherent regime, electron transport through a single molecule junction is described by the transmission coefficient, which describes how electrons pass through a molecule from one electrode to the other. Predicting features related to the transmission coefficient is a powerful tool for probing the electronic structure of molecular systems. In this connection, mid-gap transport theory is considered an efficient and easy method, which utilizes a magic ratio rule (MRR) to predict electrical conductance ratios associated with constructive quantum interference in aromatic molecules. I demonstrate that the MRR can be also applied for antiaromatic molecules and provide a comparison between the transmission coefficients of the aromatic and antiaromatic molecules. Furthermore, I present a theoretical study to investigate the transport properties of C60 using carbon-carbon triple bond anchoring groups and prove the validity of MRR when applied to such non-aromatic molecule

Exploring antiaromaticity in single-molecule junctions formed from biphenylene derivatives

We report the synthesis of a series of oligophenylene-ethynylene (OPE) derivatives with biphenylene core units, designed to assess the effects of biphenylene antiaromaticity on charge transport in molecular junctions. Analogues with naphthalene, anthracene, fluorene and biphenyl cores are studied for comparison. The molecules are terminated with pyridyl or methylthio units. Single-molecule conductance data were obtained using the mechanically controllable break junction (MCBJ) technique. It is found that when electrons pass from one electrode to the other via a phenylene ring, the electrical conductance is almost independent of the nature of the pendant π-systems attached to the phenylene ring and is rather insensitive to antiaromaticity. When electrons pass through the cyclobutadiene core of the biphenylene unit, transport is sensitive to the presence of the relatively weak single bonds connecting the two phenylene rings of biphenylene, which arise from partial antiaromaticity within the cyclobutadiene core. This leads to a negligible difference in the molecular conductance compared to the fluorene or biphenyl analogues which have standard single bonds. This ability to tune the conductance of molecular cores has no analogue in junctions formed from artificial quantum dots and reflects the quantum nature of electron transport in molecular junctions, even at room temperature

Exploring antiaromaticity in single-molecule junctions formed from biphenylene derivatives.

We report the synthesis of a series of oligophenylene-ethynylene (OPE) derivatives with biphenylene core units, designed to assess the effects of biphenylene antiaromaticity on charge transport in molecular junctions. Analogues with naphthalene, anthracene, fluorene and biphenyl cores are studied for comparison. The molecules are terminated with pyridyl or methylthio units. Single-molecule conductance data were obtained using the mechanically controllable break junction (MCBJ) technique. It is found that when electrons pass from one electrode to the other via a phenylene ring, the electrical conductance is almost independent of the nature of the pendant π-systems attached to the phenylene ring and is rather insensitive to antiaromaticity. When electrons pass through the cyclobutadiene core of the biphenylene unit, transport is sensitive to the presence of the relatively weak single bonds connecting the two phenylene rings of biphenylene, which arise from partial antiaromaticity within the cyclobutadiene core. This leads to a negligible difference in the molecular conductance compared to the fluorene or biphenyl analogues which have standard single bonds. This ability to tune the conductance of molecular cores has no analogue in junctions formed from artificial quantum dots and reflects the quantum nature of electron transport in molecular junctions, even at room temperature

Heteroatom-Induced Molecular Asymmetry Tunes Quantum Interference in Charge Transport through Single-Molecule Junctions

We studied the interplay between quantum interference (QI) and molecular asymmetry in charge transport through a single molecule. Eight compounds with five-membered core rings were synthesized, and their single-molecule conductances were characterized using the mechanically controllable break junction technique. It is found that the symmetric molecules are more conductive than their asymmetric isomers and that there is no statistically significant dependence on the aromaticity of the core. In contrast, we find experimental evidence of destructive QI in five-membered rings, which can be tuned by implanting different heteroatoms into the core ring. Our findings are rationalized by the presence of antiresonance features in the transmission curves calculated using nonequilibrium Green’s functions. This novel mechanism for modulating QI effects in charge transport via tuning of molecular asymmetry will lead to promising applications in the design of single-molecule devices

Turning the Tap: Conformational Control of Quantum Interference to Modulate Single Molecule Conductance

Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple, flexible molecular design strategies to understand, control and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta‐substituted phenylene ethylene‐type oligomers (m‐OPE) can be tuned by changing the position and conformation of pendant methoxy (OMe) substituents around the central phenylene ring. These substituents play the role of molecular‐scale ‘taps’, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic ratio and orbital product rules, and highlight a novel chemical design strategy for tuning and gating DQI features, to create single‐molecule devices with desirable electronic functions

Turning the Tap: Conformational Control of Quantum Interference to Modulate Single-Molecule Conductance.

Together with the more intuitive and commonly recognized conductance mechanisms of charge-hopping and tunneling, quantum-interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple and flexible molecular-design strategies to understand, control, and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta-substituted phenylene ethylene-type oligomers (m-OPE) can be tuned by changing the position and conformation of methoxy (OMe) substituents at the central phenylene ring. These substituents play the role of molecular-scale taps, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic-ratio and orbital-product rules, and highlight a novel chemical design strategy for tuning and gating DQI features to create single-molecule devices with desirable electronic functions

Exploring the thermoelectric properties of oligo(phenylene-ethynylene) derivatives

Seebeck coefficient measurements provide unique insights into the electronic structure of single-molecule junctions, which underpins their charge and heat transport properties. Since the Seebeck coefficient depends on the slope of the transmission function at the Fermi energy (EF), the sign of the thermoelectric voltage will be determined by the location of the molecular orbital levels relative to EF. Here we investigate thermoelectricity in molecular junctions formed from a series of oligophenylene-ethynylene (OPE) derivatives with biphenylene, naphthalene and anthracene cores and pyridyl or methylthio end-groups. Single-molecule conductance and thermoelectric voltage data were obtained using a home-built scanning tunneling microscope break junction technique. The results show that all the OPE derivatives studied here are dominated by the lowest unoccupied molecular orbital level. The Seebeck coefficients for these molecules follow the same trend as the energy derivatives of their corresponding transmission spectra around the Fermi level. The molecule terminated with pyridyl units has the largest Seebeck coefficient corresponding to the highest slope of the transmission function at EF. Density-functional-theory-based quantum transport calculations support the experimental results