The electronic efficiency and binding energy of contacts formed between graphene electrodes and poly-aromatic hydrocarbon (PAH) anchoring groups have been investigated by the non-equilibrium Green's function formalism combined with density functional theory. Our calculations show that PAH molecules always bind in the interior and at the edge of graphene in the AB stacking manner, and that the binding energy increases following the increase of the number of carbon and hydrogen atoms constituting the PAH molecule. When we move to analyzing the electronic transport properties of molecular junctions with a six-carbon alkyne chain as the central molecule, the electronic efficiency of the graphene-PAH contacts is found to depend on the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the corresponding PAH anchoring group, rather than its size. To be specific, the smaller is the HOMO-LUMO gap of the PAH anchoring group, the higher is the electronic efficiency of the graphene-PAH contact. Although the HOMO-LUMO gap of a PAH molecule depends on its specific configuration, PAH molecules with similar atomic structures show a decreasing trend for their HOMO-LUMO gap as the number of fused benzene rings increases. Therefore, graphene-conjugated molecule-graphene junctions with high-binding and high-conducting graphene-PAH contacts can be realized by choosing appropriate PAH anchor groups with a large area and a small HOMO-LUMO gap.

The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

Cu-metalated carbyne acting as a promising molecular wire The atomic structure and electronic transport properties of Cu-metalated carbyne are investigated by using the non-equilibrium Green's function formalism combined with density functional theory. Our calculations show that the incorporation of Cu atom in carbyne improves its robustness against Peierls distortion, thus to make Cu-metalated carbyne behave as a one-dimensional metal. When a finite Cu-metalated carbyne chain is connected to two (111)-oriented platinum electrodes, nearly linear current-voltage characteristics are obtained for both the atop and adatom binding sites. This is due to the efficient electronic coupling between the Cu-metalated carbyne chain and the Pt electrodes, demonstrating the promising applications of Cu-metalated carbyne chains as molecular wires in future electronic devices. Published by AIP Publishing. [http://dx

Besides the peak at one conductance quantum, G0, two additional features at ∼0.4 G0 and ∼1.3 G0 have been observed in the conductance histograms of silver quantum point contacts at room temperature in ambient conditions. In order to understand such feature, here we investigate the electronic transport and mechanical properties of clean and oxygen-doped silver atomic contacts by employing the non-equilibrium Green's function formalism combined with density functional theory. Our calculations show that, unlike clean Ag single-atom contacts showing a conductance of 1 G0, the low-bias conductance of oxygen-doped Ag atomic contacts depends on the number of oxygen impurities and their binding configuration. When one oxygen atom binds to an Ag monatomic chain sandwiched between two Ag electrodes, the low-bias conductance of the junction always decreases. In contrast, when the number of oxygen impurities is two and the O-O axis is perpendicular to the Ag-Ag axis, the transmission coefficients at the Fermi level are, respectively, calculated to be 1.44 for the junction with Ag(111) electrodes and 1.24 for that with Ag(100) electrodes, both in good agreement with the measured value of ∼1.3 G0. The calculated rupture force (1.60 nN for the junction with Ag(111) electrodes) is also consistent with the experimental value (1.66 ± 0.09 nN), confirming that the measured ∼1.3 G0 conductance should originate from Ag single-atom contacts doped with two oxygen atoms in a perpendicular configuration.

Publisher's Note: "Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes" [J. In order to address this issue, here we investigate the atomic structure and the electronic transport properties of H-bonds between two carboxylated alkanethiol molecules by employing the non-equilibrium Green's function (NEGF) formalism combined with density functional theory (DFT), i.e., the NEGF+DFT approach. [13][14][15][16][17][18][19][20][21][22] On page 174702-2, in Sec. III, right column, the two sentences beginning with "The binding energy is. . . " should be corrected as:The binding energy is calculated to be 0.67 eV, in good agreement with the benchmark value (0.68 eV) calculated at the CCSD(T)/CBS level. 12 This notation indicates that the level of electron correlation includes contributions evaluated using a coupled-cluster approach through perturbative triple excitations with a complete basis set (CBS) extrapolation.