Electronic transport properties of phenylacetylene molecular junctions

Electronic transport properties of a kind of phenylacetylene compound— (4-mercaptophenyl)-phenylacetylene are calculated by the first-principles method in the framework of density functional theory and the nonequilibrium Green's function formalism. The molecular junction shows an obvious rectifying behaviour at a bias voltage larger than 1.0 V. The rectification effect is attributed to the asymmetry of the interface contacts. Moreover, at a bias voltage larger than 2.0 V, which is not referred to in a relevant experiment [Fang L, Park J Y, Ma H, Jen A K Y and Salmeron M 2007 Langmuir 23 11522], we find a negative differential resistance phenomenon. The negative differential resistance effect may originate from the change of the delocalization degree of the molecular orbitals induced by the bias.     

Effective boundary slip and wetting characteristics of water on substrates with effects of surface morphology

ABSTRACT

In the present study, molecular dynamics (MD) simulation was used to investigate the relationship between wetting behaviour and slip length on patterned substrates. We adopted two solid surfaces of Si(100) and graphite due to similarities in their intrinsic contact angle. Contact angle and apparent slip length were obtained using discrete simulations with the same thermodynamic states. In the present study, a number of questions regarding surface roughness and the problem of contact angle (θ) and slip length (L_s) are discussed. These questions include the relationship between θ and surface roughness, the characteristics used to describe the difference between static and dynamic fluid fields and the reason for a lack of multilayer sticking observed in the current cases. Our results indicate that the quasi-universal θ ? L_s equation proposed by Hung et al. (2008) is applicable to cases involving a Cassie-like nanoscale roughened surface. In contrast, in cases with a Wenzel-like nanostructure, the no-slip boundary conditions are independent of variations in the contact angle. The adoption of a Wenzel–Cassie hybrid model helped to verify that the fluid density inside the cavity is a critical indicator of wettability of the wall–fluid interface. Our results also demonstrate that ρ_{f, cav} is a critical property in the measurement of hydrodynamic effects and thus its importance as an indicator of the validity of the equation θ ? L_s. The average time that water molecules are trapped and the number of averaged hydrogen bonds within cavities in a dynamic fluid field were also investigated.

     

Ab initio calculation of transport properties in 1,3-diphenylpropynylidene based molecular device

Using an ab initio method based on non-equilibrium Green’s functions (NEGF) combined with density functional theory (DFT), a calculation of the transport properties of a single molecular junction based on 1,3-diphenylpropynylidene (PhC₃Ph) ‘radical-π-radical’ is performed. The obvious negative differential resistance (NDR), spin current polarisation (SCP) and dual-spin current rectification (SCR) effects in this device are obtained. The total current for magnetic parallel configuration (PC) is larger at first and then less than that for magnetic antiparallel configuration (APC) as the bias increases, which suggests the abnormal magnetoresistance (MR) effect and can be used as a molecular switch with two working voltages. The evolution of the spin-polarised transmission spectrums and the frontier molecular orbitals (MOs) with applied bias is used to explain the above interesting results. Our calculations may be helpful for designing multifunctional molecular spintronics devices in the future.     

Shear viscosity of pseudo hard-spheres

We present molecular dynamics simulations of pseudo hard sphere fluid (generalized WCA potential with exponents (50, 49) proposed by Jover et al. [J. Chem. Phys 137, (2012)] using GROMACS package. The equation of state and radial distribution functions at contact are obtained from simulations and compared to the available theory of true hard spheres (HS) and available data on pseudo hard spheres. The comparison shows agreements with data by Jover et al. and the Carnahan–Starling equation of HS. The shear viscosity is obtained from the simulations and compared to the Enskog expression and previous HS simulations. It is demonstrated that the PHS potential reproduces the HS shear viscosity accurately.     

Caged H atom and H2 molecule in relation to Monte Carlo study of molecular dissociation at constant volume

Summary Analytic results for electronic kinetic energy are first presented for a hydrogen atom in a spherical cage for two radii near to the corresponding densities employed in the path-integral Monte Carlo study of isochoric molecular dissociation in dense hydrogen by Magroet al. (Magro W. R., Ceperley D. M., Pierleoni C. andBernu B.,Phys. Rev. Lett.,76 (1996) 1240). The relevance of the ?cage? results to the behaviour of dense atomic hydrogen is pointed out. Attention is then shifted to the molecular regime, and the variation with density of electronic kinetic energy for a H₂ molecule in a rigid spheroidal cage is compared and contrasted with the Monte Carlo findings. The rigid-cage model mimics this, as well as bond length contraction, under compression.     

Configuration of a chiral smectic-C film with a circular inclusion

It was shown experimentally (P.V. Dolganov et al., Europhys. Lett. 76, 250 (2006)) and by numerical calculations (C. Bohley, R. Stannarius, Eur. Phys. J. E 23, 25 (2007)) that the c -director profile of a two-dimensional chiral smectic-C (SmC) film around a circular inclusion adopts dipolar rather than quadrupolar configuration observed in achiral SmC films. We give an analytical argument on how spontaneous bend inherent in chiral SmC liquid crystals influences the configuration of a SmC liquid crystal film around a circular inclusion imposing tangential anchoring. We find how the angle α between two surface defects seen from the center of the inclusion depends on the radius of the inclusion R and the strength of the spontaneous bend q . We show, however, that the contribution of the spontaneous bend to the free energy suffers from mathematical ambiguity; it depends on the mathematical treatment of the outer boundary even when it is at infinity. This might indicate that the shape as well as the treatment of the outer boundary of the film can significantly influence the equilibrium configuration of the c -director and the position of the surface defects.     

Thermoelastic behaviour of polyvinylacetate monolayers at the air-water interface: Evidences for liquid-solid phase transition

The thermoelastic behaviour of polyvinylacetate monolayers spread on an aqueous subphase has been studied using rheological data previously published (Monroy et al., Phys. Rev. E 58, 7629 (1998)). The results show fluid-like viscoelastic behaviour well above a transition temperature , while at lower temperatures a soft solid-like behaviour emerges. The correlation between thermodynamic and elastic properties below can be described in terms of scaling laws. Received 12 January 1999 and Received in final form 11 June 1999     

Assessment of the fatigue crack closure phenomenon in damage-tolerant aluminium alloy by in-situ high-resolution synchrotron X-ray microtomography

Synchrotron X-ray microtomography has been utilized for the in-situ observation of steady-state plane-strain fatigue crack growth. A high-resolution experimental configuration and phase contrast imaging technique have enabled the reconstruction of crack images with an isotropic voxel with a 0.7 µm edge. The details of a crack are readily observed, together with evidence of the incidence and mechanical influence of closure. After preliminary investigations of the achievable accuracy and reproducibility, a variety of measurement methods are used to quantify crack-opening displacement (COD) and closure from the tomography data. Utilization of the physical displacements of microstructural features is proposed to obtain detailed COD data, and its feasibility is confirmed. Loss of fracture surface contact occurs gradually up to the maximum load. This is significantly different from tendencies reported where a single definable opening level is essentially assumed to exist. The closure behaviour is found to be attributable mainly to pronounced generation of mode III displacement which may be caused by local crack topology. Many small points of closure still remain near the crack tip, suggesting that the near-tip contact induces crack growth resistance. The effects of overloading are also discussed.     

The calculated rovibronic spectrum of scandium hydride,ScH

The electronic structure of six low-lying electronic states of scandium hydride, X?¹Σ⁺, a?³Δ, b?³Π, A?¹Δ, c?³Σ⁺ and B?¹Π, is studied using multi-reference configuration interaction as a function of bond length. Diagonal and off-diagonal dipole moment, spin–orbit coupling and electronic angular momentum curves are also computed. The results are benchmarked against experimental measurements and calculations on atomic scandium. The resulting curves are used to compute a line list of molecular rovibronic transitions for ⁴⁵ScH.     

Dynamical and structural properties of adsorbed water molecules at the TiO2 rutile-(110) surface: interfacial hydrogen bonding probed by ab-initio molecular dynamics

ABSTRACT

Ab-initio molecular dynamics (AIMD) simulations have been carried out to study a range of different and energetically-accessible adsorbed-water configurations and motifs for their vibrational and structural characteristics, in contact with rutile-(110) interfaces at 100?K. The radial pair distribution function between the titanium atoms at the interface and the hydrogen and oxygen atoms in the water monolayer show an orientation of the water molecules parallel to the surface of titania, and with hydrogen atoms pointed in the opposite direction to the surface. In some cases, a distinctive vibrational frequency region between 2500 and 3000?cm^?1 has also been observed, due to a strong dispersion interaction between water molecules. This behaviour is also seen in experimental studies of thin-film water coverage on TiO₂ surfaces.     

Pair and singlet diffusion in a Lennard-Jones liquid

Inspired by the experimental work of Richter et al. [1], we have investigated the dynamic behaviour of pairs of particles of a Lennard-Jones liquid for four different thermodynamic states. The short and long time behaviour of dynamic correlation functions of pairs are studied and directly compared with that of single particle correlation functions. Only those relating to singlet and pair diffusion are treated.

A list of the correlation functions considered in this work is presented in the table of the Appendix.

The main results are the following:

• (i)the mean square displacement of pairs of particles departs only slightly from that of single particles (doubled);

• (ii)for long times, the mean square displacement of pairs is significantly reduced when pairs from only the first coordination shell are considered;

• (iii)in the short time region the mean square displacment of pairs resembles that of single atoms, however that of pairs being initially closer than the mean separation of particles in the liquid exhibits a small tendency to lie above the doubled one of single particles.

Our results, obtained by extensive molecular dynamics (MD) calculations, are in quantitative disagreement with results generated by other authors [3, 4], and the findings of Posch et al. [6] could not be confirmed in detail by our work.     

溶液酸碱性对低聚苯亚乙炔基分子结电输运性质的影响

结合密度泛函理论和非平衡格林函数方法计算了溶液酸碱性对低聚苯亚乙炔基分子结电输运性质的影响,此低聚苯亚乙炔基分子中两个不同位置的H原子被氨基和羧基取代.通过质子化和去质子化模拟酸性溶液和碱性溶液对分子结构的影响.计算结果表明:中性环境下分子器件具有良好的导电性和微弱的整流效应;碱性溶液中羧基去质子化后,分子器件电流值增长近一倍,但整流效应变化不明显;酸性溶液中氨基质子化后,分子器件正向偏压导电性能略微降低,但整流方向发生明显反转,且与中性环境下的情况相比,整流比提高了近三倍.提出了一种利用化学手段控制分子结导电能力和整流性能的方法.     

Mechanism for giant electro-optic response of porphyrin J-aggregates in polymer film and aqueous solution

We report the dependence of the polarizability difference Δα on the orientational distribution of porphyrin J-aggregates. For quasi-one-dimensionally oriented aggregates in a polymer film, the red shift in Y ∥ F configuration was about 2 to 3 times smaller than that in Y ∥ F configuration, where Y is the orientational direction of the J-aggregates and F is the applied AC electric field vector. For an aqueous solution where J-aggregates were three-dimensionally oriented, the exciton band showed an electric-field-induced broadening. In addition, a red-shifted signal for two-dimensionally oriented aggregates in the polymer film was reduced by one order of magnitude at 77K compared with that at room temperature. These results were explained reasonably well by the molecular rearrangement model, which was applied to a variety of orientational distributions.     

A possible salicylideneanilines-based optical molecular switch induced by a reversible hydrogen transfer: an ab initio study

The electronic transport properties of the salicylideneanilines-based molecular optical switch are investigated using a nonequilibrium Green's function formalism combined with first-principles density functional theory. The molecule that comprises the switch can convert between the enol and keto tautomeric forms upon photoinduced excited state hydrogen transfer in the molecular bridge. Theoretical results show that the current through the enol form is significantly larger than that through the keto form, which realize the on and off states of the molecular switch. The physical origin of the switching behaviour is interpreted based on the spatial distributions of molecular orbitals and the HOMO-LUMO gap. Furthermore the effect of the donor/acceptor substituent on the electronic transport through the molecular device is also discussed in detail. The switching performance can be improved to some extent through the acceptor substituent.     

Electronic structure,absorption spectra,and hyperpolarisabilities of some novel push–pull zinc porphyrins. A DFT/TDDFT study

DFT/TDDFT calculations have been performed on some novel push–pull zinc porphyrins (denoted ZnPor 1, ZnPor 2, and ZnPor 3). This theoretical work aims to investigate the electronic structure, absorption spectra, and hyperpolarisabilities of these molecules. To examine the effects of the peripheral substituents on the molecular properties, zinc porphine (ZnP) and zinc tetraphenylporphine (ZnTPP) were also included in the study. The orbital energy level patterns of the substituted zinc porphyrins are indeed rather different from those of ZnP and ZnTPP. The peripheral substitution breaks the molecular D_4h symmetry of the porphyrin, thereby leading to the splitting of the absorption Q band. On the other hand, the B band in the spectra may not arise only from a single excited state; instead, it could be made up of several states that are close in energy. The calculated hyperpolarisabilities (β _vec) increase strongly from ZnPor 1 to ZnPor 2 to ZnPor3. The latter two molecules were predicted to have a large β _vec value and thus may have potential application in the development of nonlinear optical (NLO) materials.     

Magnetic relaxation phenomena in a CuMn spin glass

Experiments on the temperature and time dependence of the response function and the field cooled magnetisation of a Cu(Mn) spin glass at temperatures below the zero field spin glass temperature are used to explore the non-equilibrium nature of the underlying spin configuration. The results imply that a certain spin configuration is imprinted on the system as the temperature is decreased at a constant cooling rate. The cooling rate governs the magnitude of the FC magnetisation ((H,T)). Any intermittent halt at a constant temperature, , imprints an extended spin configuration, a process that is reflected e.g. in a downward relaxation of . On continued cooling at the same rate, the magnitude of (T) remains at a lower level than that of a continuous cooling curve. These results are put into the context of the corresponding behaviour of the response function as observed in measurements of the relaxation of the zero field cooled magnetisation. Received 27 October 1998 and Received in final form 30 November 1998     

Penetration of magnetic field into a long periodically modulated Josephson contact

A new approach to magnetic field profiling inside a Josephson contact is suggested. Its essence consists in analyzing continuous variation of a current configuration leading to a decrease in the Gibbs potential. With this approach, one can find a configuration into which the Meissner state turns when an external field slightly exceeds the upper boundary of the Meissner regime and trace the evolution of this configuration with increasing field. Calculations show that there exists critical value I _c of the pinning parameter in the range 0.95–1.00. This critical value separates two possible conditions of magnetic field penetration into the contact. At I > I _c, a near-boundary current configuration completely compensating for the external field inside the contact arises irrespective of the external field strength. At I < I _c, such a situation is observed only until the external field strength exceeds certain value H _max. Higher fields penetrate into the contact indefinitely deep. In nearboundary configurations, the magnetic field drops with increasing depth almost linearly. Its slope k has rational values, which remain constant within finite intervals of I. As I goes beyond a given interval, k rises stepwise and takes on another rational value. When an external magnetic field is switched on adiabatically, configurations with a maximal growth rate of the magnetic field are observed.     

The vicinity of an equilibrium three-phase contact line using density-functional theory: density profiles normal to the fluid interface

The paper by Nold et al. [Phys. Fluids 26 (7), 072001 (2014)] examined density profiles and the micro-scale structure of an equilibrium three-phase (liquid–vapour–solid) contact line in the immediate vicinity of the wall using elements from the statistical mechanics of classical fluids, namely density-functional theory. The present research note, building on the above work, further contributes to our understanding of the nanoscale structure of a contact line by quantifying the strong dependence of the liquid–vapour density profile on the normal distance to the interface, when compared to the dependence on the vertical distance to the substrate. A recent study by Benet et al. [J. Phys. Chem. C 118 (38), 22079 (2014)] has shown that this could explain the emergence of a film-height-dependent surface tension close to the wall, with implications for the Frumkin–Derjaguin theory.     

The short range interactions between two rare gas atoms

The short range interactions in He₂, Ne₂ and Ar₂ have been studied in terms of the electronic forces as functions of their internuclear separations employing their single configuration SCF wave functions. The results show that the constituent molecular orbitals behave differently in terms of the forces they exert on the nuclei during the interaction process. The different behaviour of the orbitals is also reflected in the redistribution of charges.