Two-photon absorption properties of aggregation systems on the basis of (E)-4-(2-nitrovinyl) benzenamine molecules

Aggregation effect caused by the intermolecular hydrogen-bonding interactions on two-photon absorption properties of (E)-4-(2-nitrovinyl) benzenamine molecules is studied at a hybrid density functional level. The geometry optimization studies indicate that there exist two probable conformations for the dimers and three for the trimers. A strong red-shift of the charge-transfer states is shown. The two-photon absorption cross sections of the molecule for certain conformations are greatly enhanced by the aggregation effect, from which a ratio of 1.0:2.6:3.6 is found for the molecule and its dimer and trimer with nearly planar structures. Namely, a 30 or 20 percent increase of the two-photon absorption cross section is observed.     

Thermo-controllable self-assembled structures of single-layer 4,4'-diamino-p-terphenyl molecules on Au(110)

Here we report the thermo-controllable self-assembled structures of single-layer 4, 4'-diamino-p-terphenyl(DAT)molecules on Au(110), which are investigated by scanning tunneling microscopy(STM) combined with density functional theory(DFT) based calculations. With the deposition of monolayer DAT molecules on Au(110) and subsequent annealing at 100℃, all DAT molecules adsorb on a(1×5) reconstructed surface with a ladder-like structure. After annealing the sample at about 200℃, STM images show three distinct domains, including DAT molecules on a(1×3) reconstructed surface, dehydrogenated molecules with two hydrogen atoms detached from one amino group(–2H-DAT) on a(1×5)reconstructed surface and dehydrogenated molecules with four hydrogen atoms detached from two amino groups(–4HDAT) on a(1×3) reconstructed surface through N–Au bonds. Furthermore, after annealing the sample to 350℃, STM image shows only one self-assembled structure with –4H-DAT molecules on a(1×3) reconstructed surface. Relative STM simulations of different self-assembled structures show excellent agreements with the experimental STM images at different annealing temperatures. Further DFT calculations on the dehydrogenation process of DAT molecule prove that the dehydrogenation barrier on a(1×5) reconstructed surface is lower than that on(1×3) one, which demonstrate the experimental results that the formation temperature of a(1×3) reconstructed surface is higher than that of a(1×5) one.     

One-colour resonant two-photon ionization spectrum of the 1-fluoronaphthalene dimer and ab initio calculation

The one-colour resonant two-photon ionization(R2PI) spectrum of the 1-fluoronaphthalene(1FN) dimer has been studied in the wavelength range of 304 to 322 nm by using a supersonic molecular beam and time-of-flight mass spectrometry.Compared with the original band 00(at 313.8 nm) of the S1 ← S0 transition of the 1FN monomer,a red-shifted band was observed in the 1FN dimer spectrum at about 315 nm with a relatively large linewidth,nearly 2 nm.Based on the consideration of inductive effect and ab initio calculations,this red-shifted band is assigned to the first electronic excited transition of the 1FN dimer.A possible geometric structure of the 1FN dimer is also obtained with calculations that the two 1FN molecules are combined through two hydrogen bonds which are formed between the hydrogen atom of a molecule and the fluorine atom of a neighbouring molecule.A time-dependent calculation was also carried out and the results are consistent with the experimental data.     

Multi-layer structures including zigzag sculptured thin films for corrosion protection of AISI 304 stainless steel

To increase corrosion resistance of the sample,its electrical impedance must be increased.Due to the fact that electrical impedance depends on elements such as electrical resistance,capacitance,and inductance,by increasing the electrical resistance,reducing the capacitance and inductance,electrical impedance and corrosion resistance can be increased.Based on the fact that these elements depend on the type of material and the geometry of the material,multilayer structures with different geometries are proposed.For this purpose,conventional multilayer thin films,multilayer thin film including zigzag structure(zigzag 1)and multilayer thin film including double zigzag structure(zigzag 2)of manganese nitride are considered to protect AISI 304 stainless steel against corrosion in salt solution.These multilayer coatings including zigzag structures are prepared by alternately using the conventional deposition of thin film and glancing angle deposition method.After deposition,the samples are placed in a furnace under nitrogen flux for nitriding.The cross sections of the structures are observed by field emission scanning electron microscopy(FESEM).Atomic force microscope(AFM)is used to make surface analyses of the samples.The results show that the multilayer thin films including zigzag structures have smaller grains than conventional multilayer thin films,and the zigzag 2 structure has the smaller grain than the other two samples,which is attributed to the effect of shadowing and porosity on the oblique angle deposition method.Crystallography structures of the samples are studied by using x-ray diffraction(XRD)pattern and the results show that nitride phase formation in zigzag 2 structure is better than that in zigzag 1 structure and conventional multilayer thin film.To investigate the corrosion resistances of the structures,electrochemical impedance spectroscopy(EIS)and potentiodynamic polarization tests are performed.The results reveal that the multilayer thin films with zigzag structures have better corrosion protection than the conventional multilayer thin films,and the zigzag structure 2 has the smallest corrosion current and the highest corrosion resistance.The electrical impedances of the samples are investigated by simulating equivalent circuits.The high corrosion resistance of zigzag 2 structure as compared with conventional multilayer structure and zigzag 1 structure,is attributed to the high electrical impedance of the structure due to its small capacitance and high electrical resistance.Finally,the surfaces of corroded samples are observed by scanning electron microscope(SEM).     

The density functional calculations on the structural and electronic properties of the endohedral fullerene dimer (N2@C60)2

The generalised gradient approximation based on density functional theory is used to study the structural and electronic properties of the endohedral fullerene dimer (N 2 @C 60) 2.Four N atoms sit at the cage centres in the form of two N 2 molecules.The density of states and Mulliken charge analysis explore that the energy levels from-6 to-10 eV are mainly influenced by the N 2 molecules.     

Three-point bending fracture characteristics of bulk metallic glasses

This paper presents the SEM micrographs for the three-point bending fracture surfaces of Zr-based, Ce-based and Mg-based bulk metallic glasses (BMGs), which show the dimple structures in the three kinds of BMGs. The shapes of the giant plastic deformation domain on the fracture surface are similar but the sizes are different. The fracture toughness KC and the dimple structure size of the Zr-based BMG are both the largest, and those of the Mg-based BMG are the smallest. The fracture toughness KC and the dimple structure size of the Ce-based BMG are between those of the Zr-based and the Mg-based BMG. Through analyzing the data of different fracture toughnesses of the BMGs, we find that the plastic zone width follows w = (KC/σY)2/(6π).     

Passivation of carbon dimer defects in amorphous SiO_2/4H–SiC(0001) interface:A first-principles study

An amorphous SiO_2/4 H–Si C(0001) interface model with carbon dimer defects is established based on density functional theory of the first-principle plane wave pseudopotential method.The structures of carbon dimer defects after passivation by H_2 and NO molecules are established,and the interface states before and after passivation are calculated by the Heyd–Scuseria–Ernzerhof(HSE06) hybrid functional scheme.Calculation results indicate that H_2 can be adsorbed on the O_2–C = C–O_2 defect and the carbon–carbon double bond is converted into a single bond.However,H_2 cannot be adsorbed on the O_2–(C = C) –O_2 defect.The NO molecules can be bonded by N and C atoms to transform the carbon–carbon double bonds,thereby passivating the two defects.This study shows that the mechanism for the passivation of Si O_2/4 H–SiC(0001) interface carbon dimer defects is to convert the carbon–carbon double bonds into carbon dimers.Moreover,some intermediate structures that can be introduced into the interface state in the band gap should be avoided.     

Atomic force microscopy investigation of growth process of organic TCNQ aggregates on SiO2 and mica substrates

<正>Deposition patterns of tetracyanoquinodimethane(TCNQ) molecules on different surfaces are investigated by atomic force microscopy.A homemade physical vapour deposition system allows the better control of molecule deposition. Taking advantage of this system,we investigate TCNQ thin film growth on both SiO_2 and mica surfaces.It is found that dense island patterns form at a high deposition rate,and a unique seahorse-like pattern forms at a low deposition rate.Growth patterns on different substrates suggest that the fractal pattern formation is dominated by molecule-molecule interaction.Finally,a phenomenal "two-branch" model is proposed to simulate the growth process of the seahorse pattern.     

Theoretical and experimental investigations of flexural wave propagation in periodic grid structures designed with the idea of phononic crystals

The propagation characteristics of flexural waves in periodic grid structures designed with the idea of phononic crystals are investigated by combining the Bloch theorem with the finite element method. This combined analysis yields phase constant surfaces, which predict the location and the extension of band gaps, as well as the directions and the regions of wave propagation at assigned frequencies. The predictions are validated by computation and experimental analysis of the harmonic responses of a finite structure with 11× 11 unit cells. The flexural wave is localized at the point of excitation in band gaps, while the directional behaviour occurs at particular frequencies in pass bands. These studies provide guidelines to designing periodic structures for vibration attenuation.     

Frequency selective surface structure optimized by genetic algorithm

Frequency selective surface (FSS) is a two-dimensional periodic structure which has prominent characteristics of bandpass or bandblock when interacting with electromagnetic waves. In this paper, the thickness, the dielectric constant, the element graph and the arrangement periodicity of an FSS medium are investigated by Genetic Algorithm (GA) when an electromagnetic wave is incident on the FSS at a wide angle, and an optimized FSS structure and transmission characteristics are obtained. The results show that the optimized structure has better stability in relation to incident angle of electromagnetic wave and preserves the stability of centre frequency even at an incident angle as large as 80°, thereby laying the foundation for the application of FSS to curved surfaces at wide angles.     

The equivalent potential of water molecules for electronic structure of lysine

In order to get more reliable electronic structures of proteins in aqueous solution, it is necessary to construct a potential of water molecules for protein’s electronic structure calculation. The lysine is a hydrophilic amino acid. It is positively charged (Lys+) in neutral water solution. The first-principles, all-electron, ab initio calcula-tions, based on the density functional theory, have been performed to construct such an equivalent potential of water molecules for lysine (Lys+). The process consists of three parts. First, the electronic structure of the cluster containing Lys+ and water molecules is calculated. By adjusting the positions of water molecules, the geometric structure of the cluster having minimum total energy is determined. Then, based on the structure, the electronic structure of Lys+ with the potential of water molecules is calculated using the self-consistent cluster-embedding (SCCE) method. Finally, the electronic structure of Lys+ with the potential of dipoles is calculated. The dipoles are adjusted so that the electronic structure of Lys+ with the potential of dipoles is close to that of water molecules. Thus the equivalent potential of water molecules for the electronic structure of lysine is obtained. The major effect of water molecules on lysine’s electronic structure is raising the occupied eigenvalues about 0.5032 eV, and broadening energy gap 89%. The effect of water molecules on the electronic structure of lysine can be simulated by dipoles potential.     

Ultraviolet laser ionization studies of 1-fluoronaphthalene clusters and density functional theory calculations

This paper studies supersonic jet-cooled 1-fluoronaphthalene(1FN) clusters by ultraviolet(UV) laser ionization at 281 nm in a time-of-flight mass spectrometer.The(1FN) + n(n=1-3) series cluster ions are observed where the signal intensity decreases with increasing cluster size.The effects of sample inlet pressures and ionization laser fluxes to mass spectral distribution are measured.Using density functional theory calculations,it obtains a planar geometric structure of 1FN dimer which is combined through two hydrogen bonds.The mass spectra indicate that the intensity of 1FN trimer is much weaker than that of 1FN dimer and this feature is attributed to the fact that the dimer may form the first "shell" in geometric structure while the larger clusters are generated based on this fundamental unit.     

Surface Structure and Reconstructions of HgTe(111) Surfaces

Hg Te(111) surface is comprehensively studied by scanning tunneling microscopy/spectroscopy(STS).In addition to th√e prim√itive(1 × 1)√ hexagonal lattice,six reconstructed surface structures are observed:(2 × 2),2 × 1,4 × 1,3 ×(1/2)3,2(1/2)2 × 2 and (1/2)11 × 2.The(2 × 2) reconstructed lattice maintains the primitive hexagonal symmetry,whi√le the lattices of the other five reconstructions are rectangular.Moreover,the topographic features of the3 ×(1/2)3 reconstruction are bias dependent,indicating that they have both topographic and electronic origins.The STSs obtained at different reconstructed surfaces show a universal dip feature with size ～100 mV,which may be attributed to the surface distortion.Our results reveal the atomic structure and complex reconstructions of the cleaved Hg Te(111) surfaces,which paves the way to understand the rich properties of Hg Te crystal.     

Fano-like resonance characteristics of asymmetric Fe_2O_3@Au core/shell nanorice dimer

A geometrical configuration of Fe2O3/Au core-shell nanorice dimer is proposed and its multipolar plasmon Fano- like resonance characteristics are theoretically investigated by generalizing the plasmon hybridization model of individual nanorice to the bright and dark modes of the nanorice dimer. Under the irradiation of polarization light, the extinction spectra of the nanorice dimer are numerically simulated by using the finite element method （FEM）. Our studies show that the Fano-like resonance of the nanorice dimer results in an asymmetric line shape of the Fano dip in the extinction spectrum which can be controlled by varying the structure parameters of the nanorice dimer. Meanwhile, there is a giant field enhancement at the gap between the two nanorices on account of the plasmonic coupling in the nanorice dimer. The aforementioned two characteristics of the nanorice dimer are useful for plasmon-induced transparency and localized surface plasmon resonance sensors.     

Stable water droplets on composite structures formed by embedded water into fully hydroxylated β-cristobalite silica

Using molecular dynamics simulations, we have revealed a novel wetting phenomenon with a droplet on composite structures formed by embedded water into(111) surface of β-cristobalite hydroxylated silica. This can be attributed to the formation of a composite structure composed of embedded water molecules and the surface hydroxyl(–OH) groups,which reduces the number of hydrogen bonds between the composite structure and the water droplet above the composite structure. Interestingly, a small uniform strain(±3%) applied to the crystal lattice of the hydroxylated silica surface can result in a notable change of the contact angles(> 40°) on the surface. The finding provides new insights into the correlation between the molecular-scale interfacial water structures and the macroscopic wettability of the hydroxylated silica surface.     

One-dimensional diffusion of vacancies on an Sr/Si(100)-c(2×4) surface

An Sr/Si(100)-c(2×4) surface is investigated by high-resolution scanning tunneling microscopy(STM) and scanning tunneling spectroscopy(STS).The semiconductor property of this surface is confirmed by STS.The STM images of this surface shows that it is bias-voltage dependent and an atomic resolution image can be obtained at an empty state under a bias voltage of 1.5 V.Furthermore,one-dimensional(1D) diffusion of vacancies can be found in the room-temperature STM images.Sr vacancies diffuse along the valley channels,which are constructed by silicon dimers in the surface.Weak interaction between Sr and silicon dimers,low metal coverage,surface vacancy,and energy of thermal fluctuation at room temperature all contribute to this 1D diffusion.     

Enhanced resistance switching stability of transparent ITO/TiO2/ITO sandwiches

We report that fully transparent resistive random access memory(TRRAM) devices based on ITO/TiO2/ITO sandwich structure,which are prepared by the method of RF magnetron sputtering,exhibit excellent switching stability.In the visible region(400-800 nm in wavelength) the TRRAM device has a transmittance of more than 80%.The fabricated TRRAM device shows a bipolar resistance switching behaviour at low voltage,while the retention test and rewrite cycles of more than 300,000 indicate the enhancement of switching capability.The mechanism of resistance switching is further explained by the forming and rupture processes of the filament in the TiO 2 layer with the help of more oxygen vacancies which are provided by the transparent ITO electrodes.     

GEOMETRIC AND ELECTRONIC STRUCTURES OF Ti8C12 CLUSTER

The electronic structure of Ti₈C₁₂ clusters with three possible geometric structures suggested in the literature is studied using the discrete-variational local-density-functional method. The results show that the ground states of the clusters are all degenerate, which means further Jahn-Teller distortions for the geometric structures of clusters. The results also indicate that the distorted dodecahedral Ti₈C₁₂ cluster, which is proposed by Guo et al. and optimized by the first principle calculations, is the most stable one among the clusters we considered and its electronic structure can explain the experimental observations. In this cluster, there is a strong pd bonding between Ti and C atoms, and the density of states at the Fermi energy is high.     

Role of buffer layer in electronic structures of iron phthalocyanine molecules on Au(111)

We investigate the electronic structures of one and two monolayer iron phthalocyanine (FePc) molecules on Au(111) surfaces. The first monolayer FePc is lying flat on the Au(111) substrate, and the second monolayer FePc is tilted at～15° relative to the substrate plane along the nearest neighbour [101ˉ] direction with a lobe downward to the central hole of the unit cell in the first layer. The structural information obtained by first-principles calculations is in agreement with the experiment results. Furthermore, it is demonstrated that the electronic structures of FePc molecules in one-monolayer FePc/Au(111) system are perturbed significantly, while the electronic structures of FePc molecules in the second monolayer in two-monolayer FePc/Au(111) system remain almost unchanged due to the screening of the buffer layer on Au(111).     

Surface effect of nanocrystals doped with rare earth ions enriched on surface and its application in upconversion luminescence

By employing a certain proportion of hydrogen peroxide, ammonia, ammonium fluoride, and ethylene diamine tetraacetic acid (EDTA) as precipitator, well-crystallized LaOF:Eu3+ and LaOF:Yb3+, Er3+ nanocrystals are synthe- sized by using the chemical co-precipitation method. The structural properties of these samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier transform infrared spectroscopy (FTIR) spectra. The results show that all the samples have an average size below 70 nm, which decreases gradually with the increase of the EDTA content, and a certain number of EDTA molecules are coupled with doped ions on the surfaces of nanocrystals. Most of the doped ions are proved to be enriched on the surfaces of nanocrystals and surrounded by the high energy vibration groups and bonds in EDTA molecules. The observed differences in upconversion emission spectrum among the different LaOF:Yb3+, Er3+ nanocrystals are explained by the different two-photon upconversion mechanisms. Especially, in the LaOF:Yb3+, Er3+ nanocrystals with EDTA, the two-photon processes that contain several special cross-relaxation processes are introduced to analyse the corresponding upconversion mechanisms.