Formation of cold bialkali dimers on helium nanodroplets

Cold alkali diatomic molecules (LiCs, NaCs) in the lowest vibrational state of the electronic triplet ground state are formed on superfluid helium nanodroplets. Using photoionization detection the excitation spectra of the transitions are recorded. The splitting of the vibrational structure in the LiCs spectrum, not observed in the NaCs spectrum, is interpreted in terms of molecular fine structure. The spectra are well reproduced by a model based on quantum chemistry potential curves including spin-orbit coupling, in combination with an asymmetric line shape function to account for cluster-induced broadening. Our refined potential curves provide important input data for the photoassociation of ultracold dipolar alkali molecules from atomic quantum gases.Received: 1 July 2004, Published online: 26 October 2004PACS: 36.40.Mr Spectroscopy and geometrical structure of clusters - 34.50.Gb Electronic excitation and ionization of molecules; intermediate molecular states (including lifetimes, state mixing, etc.) - 33.20.-t Molecular spectra     

Stabilizing oxide layers on iron particles

Pyrophoric iron powders at different stages of stabilization by oxygen (0–8% by weight) were annealed at 255 or 500°C up to 571 h. During this procedure the magnetic moments first decreased by some per cent and then increased above the initial values. The shape of the magnetic moment versus oxygen uptake curves remained unchanged. The increase of the magnetic moments as a function of time is correlated with a decrease of the specific surface area of the powders. The Mössbauer spectrum of partially stabilized powders is different from that observed on completely stabilized powders and shows a hitherto unknown magnetic iron oxide while X-ray investigations suggest this oxide to be a special iron deficient Fe₃O₄ (spinel) containing vacancies on the octahedral sites distributed at random. The spins in the oxide should then be coupled in an antiparallel way to the underlying iron core in order to explain the measured magnetic moments.     

Heterodyne holographic microscopy of gold particles

We report experimental results on heterodyne holographic microscopy of subwavelength-size gold particles. The apparatus uses continuous green-laser illumination of the metal beads in a total internal reflection configuration for dark-field operation. Detection of the scattered light at the illumination wavelength on a charge-coupled-device array detector enables 3D localization of brownian particles in water.     

Formation and destruction of nitric oxide in methane flames doped with NO at atmospheric pressure

A study of formation and destruction of NO in adiabatic laminar premixed flames of CH₄ + O₂ mixtures diluted with N₂ or Ar (with various dilution ratios) in a range of equivalence ratios at atmospheric pressure is presented. Nitric oxide was seeded into the flames using mixtures of diluent gas + 100 ppm of NO. The heat flux method was employed to measure adiabatic burning velocities of these flames. Nitric oxide concentrations in the post-flame zone at 10, 15 and 20 mm above the burner surface were measured using probe sampling. Burning velocities and NO concentrations simulated using a previously developed chemical kinetic mechanism were compared with the experimental results. The conversion ratio of NO seeded into the flames was determined. The kinetic mechanism accurately predicts burning velocities over the range of equivalence ratios and NO conversion in the rich flames. Significant discrepancies between measured and calculated NO conversion in the lean and near-stoichiometric flames were observed and discussed.     

Formation of silver particles and silver oxide plume nanocomposites upon pulsed-laser induced liquid-solid interface reaction

Nanodendrites consisting of silver and silver oxide are grown upon a pulsed-laser induced reaction at the interface between the solid target and silver nitrate solution. By using a high-resolution transmission electron microscope (HRTEM) equipped with an energy dispersive X-ray spectrometer (EDS) and selected area diffraction (SAD), the fabricated nanopatterns are identified to be a composite structure that consisting of silver nanoparticles and silver oxide nanoplumes with polycrystalline structure. In detail, these silver nanocrystals are trunks of the nanodendrite, and their size is in the range of 30 to 50 nm. The silver oxide nanoplumes are branches of the nanodendrite, and their width and length are in the ranges of 20 to 50 nm and 30 to 100 nm, respectively. Additionally, we suggested a vapor-liquid mechanism for the formation of the nanopatterns using a pulsed-laser induced liquid-solid interface reaction, in which both silver clusters in vapor and silver ions in solution are simultaneously involved.Received: 6 April 2004, Published online: 5 November 2004PACS: 81.15.Fg Laser deposition - 61.46. + w Nanoscale materials: clusters, nanoparticles, nanotubes, and nanocrystals - 81.07.Bc Nanocrystalline materials     

NO气体的空间交叉CARS

采用具有高空间分辨率的空间交叉BOX CARS相位匹配方法,完成了对NO气休室温下、Q支(v=0→v=1)振转CARS谱的测量,研究了它与NO气体压强及激光线宽的关系.从CARS基本理论出发,考虑到激光线宽及不同线型,计算出理论曲线,与实验谱线进行了比较,洛伦兹线型的理论模拟和实验结果符合较好.     

Chemisorption and decomposition of nitric oxide on ruthenium

Nitric oxide, strongly chemisorbed on ruthenium, is desorbed almost completely as oxygen and nitrogen. Oxygen, nitrogen, and nitric oxide were observed singly on ruthenium with field emission microscopy. Thermal desorption spectroscopy from Ru(101̄0) showed that molecular nitrogen is only physisorbed but nitrogen from NO decomposition is strongly chemisorbed. Nitrogen from NO shows three binding states, the most strongly bound being present to only a small extent. NO shows three and two binding states when adsorbed at 120 K and 295 K respectively. Work function measurements gave Δφ = 1.3 eV for a monolayer of NO. NO is dissociatively adsorbed above 250 K but a lower temperature limit was not established. The decomposition of NO on $\text{Ru}\text{(10}\text{1}\text{0)}$ under high vacuum conditions is catalytic in that no oxides of ruthenium were observed to form in the process.     

Physical adsorption of nitric oxide on metal oxides

Adsorption isotherms have been measured at 77.5 K for nitric oxide and nitrogen on Al₂O₃, MgO, ZnO and NiO, and at 90.2 K. for nitric oxide on A1₂O₃ and NiO. Three isotherm measurements at 77.5 K were made on the Al₂O₃ sample for each adsorbate to examine the effect of different degrees of surface dehydroxylation. The latter was assessed by means of infrared absorption studies on an Al₂O₃ disc. Isosteric heats for NO adsorption on Al₂O₃ and NiO increase from ca. 8 kJ mol^?1 and 6 kJ mol^?1 (respectively) at half monolayer coverage to near the value of the enthalpy of sublimation (16.6 kJ mol^?1) at monolayer completion. These results are discussed in terms of adsorbate dimerisation. Anomalous adsorption-desorption behaviour for the NONiO system is discussed. Effective adsorbate molecular cross-sectional areas and results for N2 adsorption on preadsorbed NO do not support the existence of either localisation or micro-porosity.     

Optical absorption in ultrafine gold particles

Optical absorption of ultrafine, gas evaporated gold particles (diameters 3—4 nm) has been measured in the wavelength interval 0.3—2.5 μm. The data agree well with the Maxwell-Garnett theory in conjunction with optical constants for bulk Au, provided these are modified to incorporate the effect of size dependent electron scattering.     

Absorption spectrum of surface-bound cap-shaped gold particles

A surface-adsorbed monolayer of cap-shaped gold particles upon submicrometer-sized polystyrene spheres exhibits pronounced absorption in the visible region. When the surrounding refractive index was altered by immersion in a fluid, the direction of the shift in the absorption spectrum was dependent on the incidence angle of the irradiation. When a thiol molecule, known to adsorb selectively on gold upon polystyrene, was added, the resultant shift in the absorption spectrum's peak was consistently toward longer wavelengths. Consequently, at certain incidence angles, a change in the refractive index of the surrounding fluid produces no shift, whereas thiol adsorption results in a clear shift, apparently reflecting the different spatial regions in which the refractive index is altered by these two procedures.     

Chemisorption of nitric oxide by nickel

The adsorption of nitric oxide on clean and pre-oxidized nickel has been investigated by X-ray photoelectron spectroscopy. Three distinct states of chemisorption have been recognised at room temperature; one is dissociative while two involve molecularly adsorbed NO. Pre-exposing the nickel surface to oxygen enabled the activity of the surface to be controlled such that adsorption was confined to only one of the molecular states. The two molecular states are suggested to arise from “bent” and “linear” forms of NO.     

In-situ XPS investigation of nitric oxide adsorption on (111), (310), and (533) gold single crystal faces

Decomposition of nitric oxide on the flat (111) and stepped (310) and (533) faces of gold single crystals was investigated by in-situ X-Ray Photoelectron Spectroscopy at elevated NO pressures up to 7 Pa and temperatures between 300 K and 500 K. The adsorbed layer formed on the gold surfaces at these conditions was found to contain nitrogen adsorbed atomically and/or nitrous oxide. The population of these adspecies was found to be dependent upon the crystal structure of the Au face, as well as the sample temperature and NO pressure. Explanations for these phenomena are discussed.     

YSZ-cells for potentiometric nitric oxide sensors

Potentiometric sensors based on zirconia can be used for determining gaseous NO at temperatures between 400 and 480 °C. For such mixed potential sensors, NO sensitive electrode materials such as CdMn₂O₄ and V₂O₅ have been described. In order to improve the cell voltage response, composite electrode materials based on V₂O₅-γ-Al₂O₃ were investigated. Sensors employing these materials show a better voltage response and an improved adhesion to the solid electrolyte compared with pure V₂O₅. The optimal temperature was found to be 440 °C. The NO sensitivity is nearly independent on the oxygen partial pressure in the gas. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Distance dependence of the interaction between single atoms: gold dimers on NiAl(110)

The importance of substrate-mediated adsorbate-adsorbate interactions on electronic states has been demonstrated for Au dimers on NiAl(110) with a scanning tunneling microscope and density functional calculations. An unoccupied resonance observed in single Au atoms splits into a doublet in Au dimers. The energy splitting depends inversely on the distance between the two adatoms, revealing the relative importance of direct and substrate-mediated interactions. Spatially resolved conductance measurements of Au dimers reveal the symmetric and antisymmetric characters of the doublet states.     

Infrared diode laser spectroscopy of nitric oxide

The lineshapes of the rotational-vibrational lines $\text{R(}\text{17}\text{2}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{, R(}\text{19}\text{2}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, and $\text{R(}\text{19}\text{2}\text{)}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ of nitric oxide were measured using a PbS_0.61Se_0.39 diode laser. These lineshapes were measured for a NO/N₂ mixture and an NO/H₂O/N₂ mixture at atmospheric pressure. This is the first high resolution spectroscopic mearuement of the rotational-vibrational lineshape of NO broadened by H₂O. The effect of the H₂O is to broaden the lines, increasing the halfwidth by up to 30% for a 10% volume concentration of H₂O. For the case of NO broadened by N₂, the measured linestrengths for the $\text{R(}\text{19}\text{2}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{R(}\text{17}\text{2}\text{)}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ lines are within 2% of previously published values.     

Formation of gold nanoparticles in gold ruby glass: The influence of tin

A ¹¹⁹Sn Mössbauer study was carried out of tin(IV) complexes with 2-benzoylpyridine thiosemicarbazone (H2Bz4DH) and its N(4)-methyl (H2Bz4M) and N(4)-phenyl (H2Bz4Ph) derivatives: [Sn(2Bz4DH)Cl₃] (1), [Sn(2Bz4DH)PhCl₂] (2), [Sn(2Bz4M)Cl₃] (3), [H₂2Bz4M]₂[Ph₂SnCl₄] (4), [Sn(2Bz4Ph)PhCl₂] (5), [Sn(2Bz4Ph)Ph₂Cl] (6), in which H2Bz4R stands for the neutral ligand and 2Bz4R stands for the anionic thiosemicarbazone. In addition, ¹¹⁹Sn Mössbauer studies of the tin(IV) complexes [Sn(H4Bz4DH)₂Cl₄H₂O] (7), [Sn(H4BzPS)₂Cl₄H₂O] (8) with 4-benzoylpyridine thiosemicarbazone (H4Bz4DH) and the correspondent semicarbazone (H4BzPS) were performed. The isomer shifts decrease upon coordination due to the variation in the percentage of s character as tin changes from approximately sp³ hybridization in the tin salts to sp³d² in the octahedral or sp³d³ in the heptahedral complexes. The Mössbauer parameters of compound (4) showed the existence of two tin(IV) sites, which have been attributed to the presence of the cis and trans isomers.     

The transition cluster-solid state in small gold particles

In small Au particles, embedded in glass, the imaginary part of the dielectric constant of the particle material and its temperature change between 300 and 1.5 K were measured as a function of particle size. Strong size dependence in a narrow size region point to a structural phase transition, probably from the cluster to the solid state, in particles of about 5 × 10² atoms, in this system.     

Formation of neutral clusters during sputtering of gold

Polycrystalline Au was bombarded with 15 keV Ar⁺, and the resulting secondary neutral cluster yield distribution was measured by laser postionisation mass spectrometry. Neutral Au_n clusters containing up to 20 atoms were observed. The yield of Au_n clusters, Y_n, was found to follow a power in n, Y_n ∝ n^−3.4, but the yield of individual clusters depended on whether n was even or odd. This odd-even yield variation was caused by fragmentation of the cluster photoions. Simulation of photoion trajectories within the TOF spectrometer shows that the fragmentation dominantly occurs before the photoions enter the reflectron part of the spectrometer.