Ab initio molecular dynamics study on Ag (n = 4, 5, 6)

Ab initio Molecular Dynamics (MD) method, based on density functional theory (DFT) with planewaves and pseudopotentials, was used to study the stability and internal motion in silver cluster Ag_n, with n =4-6. Calculations on the neutral, cationic and anionic silver dimer Ag₂ show that the bond distance and vibrational frequency calculated by DFT are of good quality. Simulations of Ag₄, Ag₅, and Ag₆ in canonical ensemble reveal distinct characteristics and isomerization paths for each cluster. At a temperature of 800 K, an Ag₄ has no definite structure due to internal motion, while for Ag₅ and Ag₆the clusters maintain the planar structure, with atomic rearrangement observed for Ag₅ but not for Ag₆. At a temperature of 200 K, Ag₄ can exist in two planar structures whilst Ag₅ is found to be stable only in the planar form. In contrast Ag₆ is stable in both planar trigonal and 3D pentagonal structures. Micro-canonical MD simulation was performed for all three clusters to obtain the vibrational density of states (DOS). Received 5 May 1999 and Received in final form 20 August 1999     

Processes in resonant domains of metal nanoparticle aggregates and optical nonlinearity of aggregates in pulsed laser fields

Optical nonlinearities in aggregates of nanoparticles formed in silver hydrosols (SHs) are studied under pico- and nanosecond pulsed laser excitation. The dependence of the nonlinear refractive index n ₂ on the degree of hydrosol aggregation is studied experimentally at the wavelength λ=1.064 μm. It is found that n ₂ changes sign when the degree of hydrosol aggregation is increased. Various physical effects occurring in resonant domains of the aggregates are analyzed using a simple physical model of two bound silver nanoparticles. The theory takes into account thermal, elastic, electrostatic, and light-induced effects. Experimental results are discussed in the context of this theory.     

Optical properties and radiation effects in layered crystals of (CnH2n+nNH3)2MCl4: n = 1, 2, 3; M = Cd,Cu, Mn

Abstract

A new absorption band has been found at 5.10 eV in (C _n H_{2n + 1}NH₃)₂CdCl₄: n = 1, 2, 3 in addition to the absorption bands of CdCl₂ whose electronic structure resembles the former crystals. The energy of the additional peak shifts with temperature by as much as 0.38 eV from 5.10eV at room temperature (RT) to 5.48 eV at liquid nitrogen temperature. This large peak shift is attributed to a structural phase transition between these two temperatures. A new type of electron center has been found in these crystals (M = Cd, Mn; n = 1, 2, 3) irradiated with X-rays at 15 K in addition to the Cl₂ ^?. This shows optical absorption bands (IR bands) in the infrared region of 10 ～ 20 kcm ^?1. The IR bands are assigned to an electron center where an electron is trapped at an ammonium site in the neighborhood of a Cl^? vacancy.     

Formation of sub-surface silver nanoparticles in silver-doped sodium–lead–germanate glass

The formation of silver nanoparticles in 60GeO₂–20PbO–20Na₂O bulk glass doped with 0.15 wt% of Ag has been studied by optical methods in the near ultraviolet-to-near infrared and mid-infrared ranges. A clear optical absorption band, which grows when increasing the annealing temperature, is observed around 460 nm, as a consequence of the surface plasmon resonance in the Ag nanoparticles. From the simultaneous analysis of optical transmittance and spectroscopic ellipsometry spectra in the near ultraviolet-to-near infrared range, it is demonstrated that the nanoparticles are surprisingly formed only in a thin layer (some tens of nm thick) underneath the sample surfaces. The potential of such a simultaneous optical analysis for determining the localization of the nanoparticles in glasses of any nature is underlined. Based on the results of a complementary mid-infrared spectroscopy characterization, the processes involved in silver migration to the surfaces and further aggregation to form nanoparticles are discussed.     

Critical conditions for spontaneous relaxation in self-organizing dissipative film systems

It is established that the necessary conditions for spontaneous relaxation of elastic strain energy in a copper-As₆₀Se₄₀ self-organizing dissipative heterostructure is that the elastic deformation energy and the temperature must reach their threshold values. It is shown that in the temperature range 270–340 K the spontaneous relaxation of elastic deformation energy is accompanied by structural-chemical ordering and anomalous diffusion of copper into the glassy chalcogenide semiconductor layer. The maximum concentration of copper dissolved in the films is 40 at. %. Conductivity inversion from p to n type is observed in doped layers obtained by this method. Zh. Tekh. Fiz. 69, 128–129 (August 1999)     

基于反转法的O2-CO2 输运性质预测

采用反转法计算得到了O₂-CO₂混合气体新的势能参数.在此基础上,根据分子动力学理论,计算了混合气体在零密度下的输运性质,包括黏度系数、热扩散系数和热扩散因子,计算的温度范围为273.15—3273.15 K.与实验值比较表明,计算结果可以满足实际工程应用.     

Thermopower in quasi-two-dimensional (BEDT-TTF) m X n organic conductors

Thermopower of (BEDT-TTF) _m X _n organic conductors has been studied using a dedicated measurement technique in the temperature range of 4.2 to 300 K. It turned out that some features of the thermopower in quasi-two-dimensional metals, namely the presence of a peak in the thermopower of α-(BEDT-TTF)₂MHg(SCN)₄ and a plateau in κ-(BEDT-TTF)₂Cu(NCS)₂ in the temperature interval between 10 and 50 K, are probably due to the phonon drag effect. Similar temperature dependences of the Seebeck coefficient can be satisfactorily interpreted in terms of a simple model taking into account the real experimental curve of the phonon heat capacity versus temperature, C ∝ T ², which is not described by the Debye formula. One feature distinguishing organic superconductors from magnetically ordered metals is a stronger temperature dependence of the characteristic electron-phonon scattering time τ _e-ph(T). Phonon drag effects also determine the behavior of the thermopower in the (BEDT-TTF)₃Cl₂·2H₂O organic conductor, which is characterized by a metal-insulator transition at T∼150 K. An analysis of measurements of the conductivity and thermopower vs. temperature taken together indicates that the transition in this compound has a complex nature: first (at T∼150 K) a metal-insulator transition occurs, which produces an energy gap in the band spectrum, then at a lower temperature (T∼20 K) a transition to a charge-density wave state takes place. Zh. éksp. Teor. Fiz. 113, 323–338 (January 1998)     

Optical properties and ultrafast electron dynamics in gold–silver alloy and core–shell nanoparticles

Silver and gold are the two most popular metals used for many nanoparticle applications, such as surface enhanced Raman scattering or surface enhanced fluorescence, in which the local field enhancement associated with the excitation of the localized surface-plasmon–polariton resonance (SPR) is exploited. Therefore, tunability of the SPR over a wide energy range is required. For this purpose we have investigated core–shell nanoparticles composed of gold and silver with different shell thicknesses as well as the impact of alloying on these nanoparticles due to a tempering process. The nanoparticles were prepared by subsequent deposition of Au and Ag atoms or vice versa on quartz substrates followed by diffusion and nucleation. Their linear extinction spectra were measured as a function of shell thickness and annealing temperature. It turned out that different gold shell thicknesses on silver cores allow a tuning of the SPR position from 2.79 to 2.05 eV, but interestingly without a significant change on the extinction amplitude. Heating of core–shell nanoparticles up to only 540 K leads to the formation of alloy nanoparticles, accompanied by a back shift of the SPR to 2.60 eV. Calculations performed in quasi-static approximation describe the experimental results quite well and prove the structural assignments of the samples. In additional experiments, we applied the well-established persistent spectral hole burning technique to the alloy nanoparticles in order to determine the ultrafast dephasing time T ₂. We obtained a dephasing time of T ₂=(8.1±1.6) fs, in good agreement with the dephasing time of T _2,∞=8.9 fs, which is already included in the dielectric function of the bulk.     

Graphene layer number dependent size distribution of silver nanoparticles

We observe that silver atoms deposited by thermal evaporation deposition onto n-layer graphene films condense upon annealing to form nanoparticles with an average diameter and density that is determined by the layer numbers of graphene films. The optical microscopy and Raman spectroscopy were utilized to identify the number of the graphene layers and the SEM (scanning electron microscopy) was used to observe the morphologies of the particles. Systematic analysis revealed that the average sizes of the nanoparticles increased with the number of graphene layers. The density of nanoparticles decreased as the number of graphene layers increased, revealing a large variation in the surface diffusion strength of nanoparticles on the different substrates. The mechanisms of formation of these layer-dependent morphologies of silver nanoparticles are related to the surface free energy and surface diffusion of the n-layer graphenes.     

Transport properties of a binary mixture of CO2ben N2 from the pair potential energy functions based on a semi-empirical inversion method

The potential energy surface of a CO₂-N₂ mixture is determined by using an inversion method, together with a new collision integral correlation [J. Phys. Chem. Ref. Data 19 1179 (1990)]. With the new invert potential, the transport properties of CO₂-N₂ mixture are presented in a temperature range from 273.15 K to 3273.15 K at low density by employing the Chapman-Enskog scheme and the Wang Chang-Uhlenbeck-de Boer theory, consisting of a viscosity coefficient, a thermal conductivity coefficient, a binary diffusion coefficient, and a thermal diffusion factor. The accuracy of the predicted results is estimated to be 2% for viscosity, 5% for thermal conductivity, and 10% for binary diffusion coefficient.     

Spectroscopic manifestations of phase changes in CaAr n clusters: finite size effects

The finite temperature optical spectroscopy of CaAr_n clusters in the range 6 n 146 is investigated using a Diatomics-In-Molecule (DIM) Hamiltonian and classical parallel tempering Monte Carlo simulations. The absorption spectrum is calculated in the vertical approximation at various temperatures between 2 K and 50 K. Several typical situations are reported. CaAr₆ shows a strong thermal broadening and shift of the spectral lines, possibly associated with isomerization. CaAr₁₃ only shows some broadening. CaAr₃₇ exhibits features corresponding to coexisting isomers at low temperature. Finally, the abrupt changes in the absorption spectrum in CaAr₁₄₆ at about 20 K are indicative of surface diffusion.     

Universal probe method for measuring the temperature of large clusters (nanoparticles) in a cluster beam

A universal probe method for measuring the temperature of large clusters (nanoparticles) in a cluster beam has been proposed and experimentally implemented. The temperature of large van der Waals clusters (nanoparticles) (CO₂) _N (where N ⩾ 10² is the number of monomers in a cluster) in the cluster beam is measured using this method with SF₆ molecules as miniature probe thermometers. The SF₆ molecules are captured by the (CO₂) _N clusters in intersecting cluster and molecular beams and sublimate from the surface of the clusters, carrying information on the velocity and temperature (internal energy) of the clusters. The velocity (kinetic energy) of SF₆ molecules sublimating from the surface of the clusters has been measured by the time-of-flight method and the temperature of the clusters has been determined as T _cl = (105 ± 15) K.     

Ion beam mixing and liquid interdiffusion

Abstract

A characteristic of ion mixing in the low temperature portion of the thermally assisted ion mixing regime is that the activation energy obtained from most experiments is in the range of 0.1 to 0.3 eV. These values are typically a factor of 4 to 10 lower than the vacancy migration energy of most elements. This discrepancy is maintained even when the ion mixing data is contrasted to the more comparable data from concentrated homogeneous alloys. It appears that an explanation of the ion mixing activation energy is not possible by radiation enhanced diffusion (RED) where, at the low temperature end of RED, defect annihilation is by direct vacancy-interstitial recombination and the predicted activation energy is Q = 0.5 E^M _v

In an attempt to understand the origin of the low activation energies obtained during ion mixing we have performed calculations of the mutual diffusion coefficients in binary liquid mixtures. A hard sphere fluid model based on the kinetic gas theory of Enskog was used. The model was corrected to agree with molecular dynamic calculations of liquid state diffusion and included thermodynamic driving forces. The calculations resulted in temperature dependent mixing curves which are in good agreement with ion mixing experiments and suggested that the temperature rise in the thermal spike approximately ranged between 1000 and 4000 K.     

Electron heating in a submicron-size n GaAs wire

We have studied electron heating in a submicron-size GaAs wire from 4.2 K to 50 K. We find that the energy relaxation rate for the electrons is of the form τ_E⁻¹ = α + βT_eⁿ where α, β are constants and T_e is the electron temperature. We associate the temperature-independent term with a quasi-elastic surface scattering process in which an electron losses 1% of its energy at each collision. The temperature dependent term may be due to electron-phonon scattering. It is possible to fit the data to 2 < n < 3.     

Synthesis of MoO2 particles during oxidation of bulk molybdenum samples by supercritical water

It was found that bulk samples of molybdenum 〈Mo〉 are oxidized by supercritical water forming nanoparticles of monocline MoO₂. The average size of nanoparticles obtained at uniform heating of 〈Mo〉 with supercritical water was about 27 nm, and the size of agglomerates of nanoparticles was ≤ 1 μm. From time dependence of the amount of formed H₂ n _H2(t), we have determined kinetic parameters of 〈Mo〉 transition to MoO₂ particles. The dependence dn _H2/dt is characterized by the presence of two pronounced maxima. This is explained by the change of mutual diffusion of H₂ and H₂O molecules along with the growth of thickness of the layer of MoO₂ nanoparticles.     

The Effect of Temperature on the Particle Sizes and the Recrystallization of Silver Sulfide Nanopowders

The recrystallization of silver sulfide Ag₂S nanoparticles has been studied and the range of the thermal stability of the nanoparticle sizes has been determined. Nanopowders Ag₂S with particle sizes of 45–50 nm were obtained by chemical deposition from aqueous solutions. To study the thermal stability of the Ag₂S nanoparticle sizes, the nanocrystalline powders have been annealed in a vacuum of 0.01 Pa on heating from room temperature to 493 K and in argon at 623 K. Annealing up to a temperature of 453 K leads to insignificant nanoparticle growth and annealing of microstrains, which allows one to consider this temperature range as the region of thermal stability of the silver sulfide nanostate. The temperature range from 450 to 900 K, in which the particle size increases by a factor of 3–6, corresponds to the temperature of collective recrystallization of the silver sulfide nanopowder.     

The effect of silver on the optical,spectral-luminescent,and crystallization properties of bromide photo-thermo-refractive glasses

The effect of silver on the optical, spectral-luminescent, and crystallization properties of bromide photo-thermo-refractive glasses is studied. Multicomponent photosensitive glasses of the Na₂O–ZnO–Al₂O₃–SiO₂ system with photosensitizing agents (cerium, antimony, silver) and halogenides (fluorine and bromine) are synthesized. Ultraviolet irradiation and thermal treatment below the glass-transition temperature of the glasses cause the formation of silver molecular clusters, which exhibit luminescence in the visible and infrared regions. UV irradiation and thermal treatment of glasses above the glass-transition temperature lead to the growth of silver nanoparticles with plasmon resonance peak in the region of 420 nm. Further thermal treatment of glasses above the glass-transition temperature shifts the plasmon-resonance maximum by 70 nm to longer wavelengths, which is related to the growth of a crystalline shell consisting of mixed silver and sodium bromides on nanoparticles. This formation of a crystalline phase on colloidal centers results in a local increase in the refractive index of the irradiated region by +Δn ~ 900 ppm compared to the nonirradiated region. Photo-thermo-refractive glasses with increased silver concentration are promising photosensitive materials for creating holographic optical elements and devices for line narrowing and stabilizing filters, spectral beam combiners, and filters for increasing the spectral brightness of laser diodes. A positive change in the refractive index of Photo-thermo-refractive glasses provides the possibility of recording in them 3D waveguide and integrated-optical structures.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.     

Physical properties of the homologous series Y2Ba4Cu6+nO14+n (n=0,1,2) at high pressure

Abstract

We have measured resistivity and magnetic susceptibility of Y₂Ba₄Cu_6+nO_14+n (n=0,1,2) on bulk material and single crystals as well. We have found a pressure dependence of dT_c/dp within the range of 0.05 to 0.55 K/kbar depending on the symmetry.     

Structure and transport properties of stephanite (Ag5SbS4) according to antimony nuclear quadrupole resonance

Silver sulfo-antimonide Ag₅SbS₄ (stephanite) has been studied by nuclear quadrupole resonance (NQR) spectroscopy on antimony nuclei. The temperature dependences of the spectroscopic and relaxation parameters have been examined in the range of 4.2?C395 K. A phase transition at 140 K and internal motions with an activation energy of 0.29 eV have been experimentally detected. The nature of the phase transition and diffusion of silver ions has been discussed in view of the reported data.