Guang-Ping Zhang

Stretch or contraction induced inversion of rectification in diblock molecular junctions

Based on ab initio theory and nonequilibrium Greens function method, the effect of stretch or contraction on the rectification in diblock co-oligomer molecular diodes is investigated theoretically. Interestingly, an inversion of rectifying direction induced by stretching or contracting the molecular junctions, which is closely related to the number of the pyrimidinyl-phenyl units, is proposed. The analysis of the molecular projected self-consistent Hamiltonian and the evolution of the frontier molecular orbitals as well as transmission coefficients under external biases gives an inside view of the observed results. It reveals that the asymmetric molecular level shift and asymmetric evolution of orbital wave functions under biases are competitive mechanisms for rectification. The stretching or contracting induced inversion of the rectification is due to the conversion of the dominant mechanism. This work suggests a feasible technique to manipulate the rectification performance in molecular diodes by use of the mechanically controllable method.

Length-dependent inversion of rectification in diblock co-oligomer diodes

The rectifying direction of diblock co-oligomer molecular diodes is investigated theoretically by analyzing the asymmetric bias effects on the molecular orbitals. The results reveal two competitive mechanisms in determining the rectifying direction, asymmetric energy shift of eigenstates and asymmetric spatial localization of wave functions upon the reversal of bias voltage. It is demonstrated that the dominated mechanism may be converted between the two mechanisms by changing the molecular length, which induces an inversion of the rectification. This work indicates the relative orientation of the two moieties is not sufficient to decide the rectifying direction of co-oligomer diodes.

Rectifying Properties of Oligo(Phenylene Ethynylene) Heterometallic Molecular Junctions: Molecular Length and Side Group Effects

The rectifying properties of α,ω-dithiol terminated oligo(phenylene ethynylene) molecules sandwiched between heterometallic electrodes, including the molecular length and side group effects, are theoretically investigated using the fully self-consistent nonequilibrium Greens function method combined with density functional theory. The results show nonlinear variation with changes in molecule length: when the molecule becomes longer, the current decreases at first and then increases while the rectification shifts in the opposite direction. This stems from the change in molecular eigenstates and the coupling between the molecule and electrodes caused by different molecular lengths. The rectifying behavior of heterometallic molecular junctions can be attributed to the asymmetric molecule-electrode contacts, which lead to asymmetric electronic tunneling spectra, molecular eigenvalues, molecular orbitals, and potential drop at reversed equivalent bias voltages. Our results provide a fundamental understanding of the rectification of heterometallic molecular junction, and a prediction of rectifiers with different rectification properties from those in the experiment, using electrodes with reduced sizes.

Effect of Gate Electric Field on Single Organic Molecular Devices

Based on the first‐principles computational method and elastic scattering Greens function theory, we have investigated the effect of gate electric field on electronic transport properties of a series of single organic molecular junctions theoretically. The numerical results show that the molecular junctions that have redox centers and relatively large dipole moments parallel gate direction can respond to the gate electric field remarkably. The current‐voltage properties of 2,5‐dimethyl‐thiophene‐dithiol present N‐channel‐metal‐oxide‐semiconductor‐like characteristics. Its distinct current‐voltage properties can be understood from the evolution of eigenvalues, coupling energies, and atomic charges with gate electric field.

Strong Fermi level pinning induces a high rectification ratio and negative differential resistance in hydrogen bonding bridged single cytidine pair junctions

We propose a high performance single molecule rectifier by sandwiching a deoxycytidine base pair between gold electrodes. The conductance of the single base pair junction can be controlled by its protonation status, with ON/OFF ratios between the protonated (pCC) and deprotonated (CC) junctions of 3-5 orders of magnitude. In the conducting pCC state, we observed a high rectification ratio of two orders of magnitude at bias voltage values around 0.1 V. This rectification ratio surpasses most of the theoretical designs for single molecular rectifiers, while the low working voltage implies significant energy efficiency. Negative differential resistance (NDR) was also witnessed in the protonated state, with a peak to valley ratio of 24. Both the rectifying and NDR effects originate from strong Fermi level pinning effects. The electronic performance offers these single base pair junctions potential applications as a unimolecular rectifier or switch with an NDR effect. The current-voltage response is unique compared with those of the reported canonical A-T and G-C pairs, and provides the possibility to be used for i-motif DNA structure recognition or sequencing.

Designing molecular rectifiers and spin valves using metallocene-functionalized undecanethiolates: one transition metal atom matters

By using the first-principles method, here we have theoretically investigated the effects of the head group on the rectifying and spin filtering properties of metallocenyl-functionalized undecanethiolate molecular junctions. It is found that the rectifying performance as well as the rectification direction of the molecular junctions can be largely modulated by choosing different metallocenyl head groups, i.e., chromocene (CrCp2), manganocene (MnCp2), ferrocene (FeCp2), cobaltocene (CoCp2), and nickelocene (NiCp2). More interestingly, large or even perfect spin filtering efficiency can be obtained for molecular junctions embedded with a magnetic metallocenyl head group (CrCp2, MnCp2, CoCp2, or NiCp2). Further analysis reveals that all of the frontier molecular orbitals around the Fermi energy are localized on the metallocenyl head group, which results in their monotonic evolutions under positive and negative bias voltage due to the electrostatic effect of external bias voltage. This contributes to the rectification observed for the molecular junctions. Meanwhile, alignments of the frontier molecular orbitals with respect to the Fermi energy and their spin properties can be dramatically changed by the metallocenyl head group, which essentially leads to the inversion of rectification direction and the remarkable spin filtering effect. Our result provides a feasible way to optimize the rectifying performance of alkanethiolate based molecular diodes, and it also suggests a good platform to obtain a high or even perfect spin filtering efficiency that has a wide use in the field of molecular spintronics.

Towards Rectifying Performance at the Molecular Scale

Molecular diode, proposed by Mark Ratner and Arieh Aviram in 1974, is the first single-molecule device investigated in molecular electronics. As a fundamental device in an electric circuit, molecular diode has attracted an enduring and extensive focus during the past decades. In this review, the theoretical and experimental progresses of both charge-based and spin-based molecular diodes are summarized. For the charge-based molecular diodes, the rectifying properties originated from asymmetric molecules including D–σ–A, D–π–A, D–A, and σ–π type compounds, asymmetric electrodes, asymmetric nanoribbons, and their combination are analyzed. Correspondingly, the rectification mechanisms are discussed in detail. Furthermore, a series of strategies for modulating rectification performance is figured out. Discussion on concept of molecular spin diode is also involved based on a magnetic co-oligomer. At the same time, the intrinsic mechanism as well as the modulation of the spin-current rectification performance is introduced. Finally, several crucial issues that need to be addressed in the future are given.

The effect of Duschinsky rotation on charge transport properties of molecular junctions in the sequential tunneling regime

We present here a systematic theoretical study on the effect of Duschinsky rotation on charge transport properties of molecular junctions in the sequential tunneling regime. In the simulations we assume that only two electronic charging states each coupled to a two dimensional vibrational potential energy surface (PES) are involved in the transport process. The Duschinsky rotation effect is accounted by varying the rotational angle between the two sets of displaced PESs. Both harmonic potential and anharmonic Morse potential have been considered for the cases of the intermediate to strong electron-vibration couplings. Our calculations show that the inclusion of the Duschinsky rotation effect can significantly change the charge transport properties of a molecular junction. Such an effect makes the otherwise symmetric Coulomb diamond become asymmetric in harmonic potentials. Depending on the angle of the rotation, the low bias current could be significantly suppressed or enhanced. This effect is particularly prominent in the Franck-Condon (FC) blockade regime where the electron-vibration coupling is strong. These changes are caused by the variation of the FC factors which are closely related to the rotational angle between the two sets of PESs involved in the charge transport process. For a molecular junction with Morse potentials, the changes caused by Duschinsky rotation are much more complicated. Both the amplitude and shape of the Coulomb diamond are closely dependent on the rotational angle in the whole range from 0 to 2π. One interesting result is that with a rotation angle of π (and also π/2 for certain cases) symmetric Coulomb diamonds can even be formed from the intrinsically asymmetric Morse potential. These results could be important for the interpretation of experimental observations.

Effect of H 2 O Adsorption on Negative Differential Conductance Behavior of Single Junction

Large negative differential conductance (NDC) at lower bias regime is a very desirable functional property for single molecular device. Due to the non-conjugated segment separating two conjugated branches, the single thiolated arylethynylene molecule with 9,10-dihydroanthracene core (denoted as TADHA) presents excellent NDC behavior in lower bias regime. Based on the ab initio calculation and non-equilibrium Green’s function formalism, the NDC behavior of TADHA molecular device and the H2O-molecule-adsorption effects are studied systematically. The numerical results show that the NDC behavior of TADHA molecular junction originates from the Stark effect of the applied bias which splits the degeneration of the highest occupied molecular orbital (HOMO) and HOMO-1. The H2O molecule adsorbed on the terminal sulphur atom strongly suppresses the conductance of TADHA molecular device and destroys the NDC behavior in the lower bias regime. Single or separated H2O molecules adsorbed on the backbone of TADHA molecule can depress the energy levels of molecular orbitals, but have little effects on the NDC behavior of the TADHA molecular junction. Aggregate of several H2O molecules adsorbed on one branch of TADHA molecule can dramatically enhance the conductance and NDC behavior of the molecular junction, and result in rectifier behavior.

Effect of molecular conformations on the electronic transport in oxygen-substituted alkanethiol molecular junctions

The relationship between the molecular structure and the electronic transport properties of molecular junctions based on thiol-terminated oligoethers, which are obtained by replacing every third methylene unit in the corresponding alkanethiols with an oxygen atom, is investigated by employing the non-equilibrium Greens function formalism combined with density functional theory. Our calculations show that the low-bias conductance depends strongly on the conformation of the oligoethers in the junction. Specifically, in the cases of trans-extended conformation, the oxygen-dominated transmission peaks are very sharp and well below the Fermi energy, EF, thus hardly affect the transmission around EF; the Au-S interface hybrid states couple with σ-bonds in the molecular backbone forming the conduction channel at EF, resulting in a conductance decay against the molecular length close to that for alkanethiols. By contrast, for junctions with oligoethers in helical conformations, some π-type oxygen orbitals coupling with the Au-S interface hybrid states contribute to the transmission around EF. The molecule-electrode electronic coupling is also enhanced at the non-thiol side due to the specific spatial orientation introduced by the twist of the molecular backbone. This leads to a much smaller conductance decay constant. Our findings highlight the important role of the molecular conformation of oligoethers in their electronic transport properties and are also helpful for the design of molecular wires with heteroatom-substituted alkanethiols.