Size Modulation of Colloidal Au Nanoparticles via Digestive Ripening in Conjunction with a Solvated Metal Atom Dispersion Method: An Insight Into Mechanism

Digestive ripening, a postsynthetic treatment of colloidal nanoparticles, is a versatile method to produce monodisperse nanoparticles and to prepare various bimetallic nanostructures. The mechanism of this process is largely unknown. Herein, we present a systematic study conducted using Au nanoparticles prepared by a solvated metal atom dispersion method to probe the mechanistic aspects of digestive ripening. In our study, experimental conditions such as concentration of capping agent, reaction time, and temperature, were found to influence the course of the digestive ripening process. Here it is shown that, during digestive ripening under reflux, nanoparticles within an optimum size window are conserved, and surface etching facilitated mass transfer resulted in monodisperse nanoparticles. Overall, digestive ripening can be considered as a kinetically controlled thermodynamic process.

Synthesis and crystal structure of copper (II) uracil ternary polymeric complex with 1,10-phenanthroline along with the Hirshfeld surface analysis of the metal binding sites for the uracil ligand

The study of models for ``metal-enzyme-substrate'' interaction has been a proactive area of research owing to its biological and pharmacological importance. In this regard the ternary copper uracil complex with 1,10-phenanthroline represents metal-enzyme-substrate system for DNA binding enzymes. The synthesis of the complex, followed by slow evaporation of the reaction mixture forms two concomitant solvatomorph crystals viz., {Cu(phen)(mu-ura)(H2O)](n)center dot H2O (1a)} and {Cu(phen)(mu-ura)(H2O)](n)center dot CH3OH (1b)}. Both complexes are structurally characterized, while elemental analysis, IR and EPR spectra were recorded for 1b (major product). In both complexes, uracil coordinates uniquely via N1 and N3 nitrogen atom acting as a bidentate bridging ligand forming a 1-D polymer. The two solvatomorphs were quantitatively analyzed for the differences with the aid of Hirshfeld surface analysis. (C) 2014 Elsevier B.V. All rights reserved.

Atomistic investigation of the effects of temperature and surface roughness on diffusion bonding between Cu and Al

Molecular dynamics (MD) simulations are carried out to analyze the diffusion bonding at Cu/Al interfaces. The results indicate that the thickness of the interfacial layer is temperature-dependent, with higher temperatures yielding larger thicknesses. At temperatures below 750 K, the interface thickness is found to increase in a stepwise manner as a function of time. At temperatures above 750 K, the thickness increases rapidly and smoothly. When surface roughness is present, the bonding process consists of three stages. In the first stage, surfaces deform under stress, resulting in increased contact areas. The second stage involves significant plastic deformation at the interface as temperature increases, resulting in the disappearance of interstices and full contact of the surface pair. The last stage entails the diffusion of atoms under constant temperature. The bonded specimens show tensile strengths reaching 88% of the ideal Cu/Al contact strength. (c) 2007 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The organometallic chemistry of the Ru(001) surface

The organometallic chemistry of the hexagonally close-packed Ru(001) surface has been studied using electron energy loss spectroscopy and thermal desorption mass spectrometry. The molecules that have been studied are acetylene, formamide and ammonia. The chemistry of acetylene and formamide has also been investigated in the presence of coadsorbed hydrogen and oxygen adatoms.

Acetylene is adsorbed molecularly on Ru(001) below approximately 230 K, with rehybridization of the molecule to nearly sp^3 occurring. The principal decomposition products at higher temperatures are ethylidyne (CCH_3) and acetylide (CCH) between 230 and 350 K, and methylidyne (CH) and surface carbon at higher temperatures. Some methylidyne is stable to approximately 700 K. The preadsorption of hydrogen does not alter the decomposition products of acetylene, but reduces the saturation coverage and also leads to the formation of a small amount of ethylene (via an η^2-CHCH_2 species) which desorbs molecularly near 175 K. Preadsorbed oxygen also reduces the saturation coverage of acetylene but has virtually no effect on the nature of the molecularly chemisorbed acetylene. It does, however, lead to the formation of an sp^2-hybridized vinylidene (CCH_2) species in the decomposition of acetylene, in addition to the decomposition products that are formed on the clean surface. There is no molecular desorption of chemisorbed acetylene from clean Ru(001), hydrogen-presaturated Ru(001), or oxygen-presaturated Ru(001).

The adsorption and decomposition of formamide has been studied on clean Ru(001), hydrogen-presaturated Ru(001), and Ru(001)-p(1x2)-O (oxygen adatom coverage = 0.5). On clean Ru(001), the adsorption of low coverages of formamide at 80 K results in CH bond cleavage and rehybridization of the carbonyl double bond to produce an η^2 (C,O)-NH_2CO species. This species is stable to approximately 250 K at which point it decomposes to yield a mixture of coadsorbed carbon monoxide, ammonia, an NH species and hydrogen adatoms. The decomposition of NH to hydrogen and nitrogen adatoms occurs between 350 and 400 K, and the thermal desorption products are NH_3 (-315 K), H_2 (-420 K), CO (-480 K) and N_2 (-770 K). At higher formamide coverages, some formamide is adsorbed molecularly at 80 K, leading both to molecular desorption and to the formation of a new surface intermediate between 300 and 375 K that is identified tentatively as η^1(N)-NCHO. On Ru(001)- p(1x2)-O and hydrogen-presaturated Ru(001), formamide adsorbs molecularly at 80 K in an η^1(O)- NH_2CHO configuration. On the oxygen-precovered surface, the molecularly adsorbed formamide undergoes competing desorption and decomposition, resulting in the formation of an η^2(N,O)-NHCHO species (analogous to a bidentate formate) at approximately 265 K. This species decomposes near 420 K with the evolution of CO and H_2 into the gas phase. On the hydrogen precovered surface, the Η^1(O)-NH_2CHO converts below 200 K to η^2(C,O)-NH_2CHO and η^2(C,O)-NH^2CO, with some molecular desorption occurring also at high coverage. The η^2(C,O)-bonded species decompose in a manner similar to the decomposition of η^2(C,O)-NH_2CO on the clean surface, although the formation of ammonia is not detected.

Ammonia adsorbs reversibly on Ru(001) at 80 K, with negligible dissociation occurring as the surface is annealed The EEL spectra of ammonia on Ru(001) are very similar to those of ammonia on other metal surfaces. Off-specular EEL spectra of chemisorbed ammonia allow the v(Ru-NH_3) and ρ(NH_3) vibrational loss features to be resolved near 340 and 625 cm^(-1), respectively. The intense δ_g (NH_3) loss feature shifts downward in frequency with increasing ammonia coverage, from approximately 1160 cm^(-1) in the low coverage limit to 1070 cm^(-1) at saturation. In coordination compounds of ammonia, the frequency of this mode shifts downward with decreasing charge on the metal atom, and its downshift on Ru(001) can be correlated with the large work function decrease that the surface has previously been shown to undergo when ammonia is adsorbed. The EELS data are consistent with ammonia adsorption in on-top sites. Second-layer and multilayer ammonia on Ru(001) have also been characterized vibrationally, and the results are similar to those obtained for other metal surfaces.

I. Quantum mechanics of one-dimensional two-particle models. II. A quantum mechanical treatment of inelastic collisions

Part I

Solutions of Schrödinger’s equation for system of two particles bound in various stationary one-dimensional potential wells and repelling each other with a Coulomb force are obtained by the method of finite differences. The general properties of such systems are worked out in detail for the case of two electrons in an infinite square well. For small well widths (1-10 a.u.) the energy levels lie above those of the noninteresting particle model by as much as a factor of 4, although excitation energies are only half again as great. The analytical form of the solutions is obtained and it is shown that every eigenstate is doubly degenerate due to the “pathological” nature of the one-dimensional Coulomb potential. This degeneracy is verified numerically by the finite-difference method. The properties of the square-well system are compared with those of the free-electron and hard-sphere models; perturbation and variational treatments are also carried out using the hard-sphere Hamiltonian as a zeroth-order approximation. The lowest several finite-difference eigenvalues converge from below with decreasing mesh size to energies below those of the “best” linear variational function consisting of hard-sphere eigenfunctions. The finite-difference solutions in general yield expectation values and matrix elements as accurate as those obtained using the “best” variational function.

The system of two electrons in a parabolic well is also treated by finite differences. In this system it is possible to separate the center-of-mass motion and hence to effect a considerable numerical simplification. It is shown that the pathological one-dimensional Coulomb potential gives rise to doubly degenerate eigenstates for the parabolic well in exactly the same manner as for the infinite square well.

Part II

A general method of treating inelastic collisions quantum mechanically is developed and applied to several one-dimensional models. The formalism is first developed for nonreactive “vibrational” excitations of a bound system by an incident free particle. It is then extended to treat simple exchange reactions of the form A + BC →AB + C. The method consists essentially of finding a set of linearly independent solutions of the Schrödinger equation such that each solution of the set satisfies a distinct, yet arbitrary boundary condition specified in the asymptotic region. These linearly independent solutions are then combined to form a total scattering wavefunction having the correct asymptotic form. The method of finite differences is used to determine the linearly independent functions.

The theory is applied to the impulsive collision of a free particle with a particle bound in (1) an infinite square well and (2) a parabolic well. Calculated transition probabilities agree well with previously obtained values.

Several models for the exchange reaction involving three identical particles are also treated: (1) infinite-square-well potential surface, in which all three particles interact as hard spheres and each two-particle subsystem (i.e. BC and AB) is bound by an attractive infinite-square-well potential; (2) truncated parabolic potential surface, in which the two-particle subsystems are bound by a harmonic oscillator potential which becomes infinite for interparticle separations greater than a certain value; (3) parabolic (untruncated) surface. Although there are no published values with which to compare our reaction probabilities, several independent checks on internal consistency indicate that the results are reliable.

X-RAY-SCATTERING FROM A ROUGH-SURFACE AND DAMAGED LAYER OF POLISHED WAFERS

Theoretical and experimental investigations were performed to show the application of x-ray crystal truncation rod scattering combined with x-ray reflectivity in the measurements of surface roughness and near-surface damage of mechanochemically polished wafers. By fitting the measured crystal truncation rod curves it has been shown that polished wafers are divided into three parts -irregular steps on the surface, a damaged thin layer beneath the surface and a perfect bulk. The results show that the root mean square of the surface roughness of mechanochemically polished Fe-doped and/or S-doped InP wafers is one to two atom layers, and that the lateral correlation length of the surface roughness is about 3000-7500 Angstrom. The thickness of the damaged region is found to be about 1000 atom layers.

High negative ion production yield in 30 keV F2+ + adenine (C5H5N5) collisions

In collisions between slow F2+ ions (30 keV) and molecular targets, adenine, scattered particle production yields have been measured directly by simultaneous detection of neutrals, positive and negative ions. The relative cross-section for a negative ion formation channel was measured to be 1%. Despite a slight decrease compared to a larger target, the fullerene C-60, the measured negative ion formation cross section is still at least one order of magnitude larger than the yield in ion-atom interactions.

One-electron capture with simultaneous ionization in Cq+, Oq+ (q=1-4)-Ar collisions

The ratios R-k1 of k-fold to single ionization of the target atom with simultaneous one-electron capture by the projectile have been measured for 15-480 keV/u (nu(p) = 0.8-4.4 a.u.) collisions of Cq+, Oq+ (q=1-4) with Ar, using time-of-flight techniques which allowed the simultaneous identification of the final charge state of both the low-velocity recoil ion and the high-velocity projectile for each collision event. The present ratios are similar to those for He+ and He2+ ion impact. The energy dependence of R-k1 shows a maximum at a certain energy, E-max. which approximately conforms to the q(1/2)-dependence scaling. For a fixed projectile state, the ratios R-k1 also vary strongly with outgoing reaction channels. The general behavior of the measured data can be qualitatively analyzed by a simple impact-parameter, independent-electron model. (C) 2009 Elsevier B.V. All rights reserved.

X-ray spectra induced by slow highly charged Arq+ ions in collision with Nb surface

The X-ray spectra of Nb surface induced by Arq+ (q = 16,17) ions with the energy range from 10 to 20 keV/q were studied by the optical spectrum technology. The experimental results indicate that the multi-electron excitation occurred as a highly charged Ar16+ ion was neutralized below the metal surface. The K shell electron of Ar16+ was excited and then de-excited cascadly to emit K X-ray. The intensity of the X-ray emitted from K shell of the hollow Ar atom decreased with the increase of projectile kinetic energy. The intensity of the X-ray emitted from L shell of the target atom Nb increased with the increase of projectile kinetic energy. The X-ray yield of Ar17+ is three magnitude orders larger than that of Ar16+.

The coulomb potential energy effect on the intensity of the characteristic lines at highly charged ion incendence on Al surface

The Al atomic characteristic spectral lines were induced by the impact of Ar-40(q+) ions (8 <= q <= 16; kinetic energy 150 keV) on Al surface. The result shows that by Penning impinging and resonant capture, the ion energy is deposited on the Al surface to excite the target atom, which is different from light excitation. Not only are the transitions betweem electronic configurations of the atomic complex excited, but the enhancing tendency of the characteristic spectral line intensity is consistent with the enhancing tendency of the coulomb potential energy of the incident ions with increasing charged states.

Slow isocharged sequence ions with helium collisions: Projectile core dependence

The collisions of the isocharged sequence ions of q=6 (C6+, N6+, O6+, F6+, Ne6+, Ar6+, and Ca6+), q=7 (F7+, Ne7+, S7+, Ar7+, and Ca7+), q=8 (F8+, Ne8+, Ar8+, and Ca8+), q=9 (F9+, Ne9+, Si9+, S9+, Ar9+, and Ca9+) and q=11 (Si11+, Ar11+, and Ca11+) with helium at the same velocities were investigated. The cross-section ratios of the double-electron transfer (DET) to the single-electron capture (SEC) sigma(DET)/sigma(SEC) and the true double-electron capture (TDC) to the double-electron transfer sigma(TDC)/sigma(DET) were measured. It shows that for different ions in an isocharged sequence, the experimental cross-section ratio sigma(DET)/sigma(SEC) varies by a factor of 3. The results confirm that the projectile core is another dominant factor besides the charge state and the collision velocity in slow (0.35-0.49v(0); v(0) denotes the Bohr velocity) highly charged ions (HCIs) with helium collisions. The experimental cross-section ratio sigma(DET)/sigma(SEC) is compared with the extended classical over-barrier model (ECBM) [A. Barany , Nucl. Instrum. Methods Phys. Res. B 9, 397 (1985)], the molecular Coulombic barrier model (MCBM) [A. Niehaus, J. Phys. B 19, 2925 (1986)], and the semiempirical scaling laws (SSL) [N. Selberg , Phys. Rev. A 54, 4127 (1996)]. It also shows that the projectile core properties affect the initial capture probabilities as well as the subsequent relaxation of the projectiles. The experimental cross-section ratio sigma(TDC)/sigma(DET) for those lower isocharged sequences is dramatically affected by the projectile core structure, while for those sufficiently highly isocharged sequences, the autoionization always dominates, hence the cross-section ratio sigma(TDC)/sigma(DET) is always small.

K-shell ionization cross section of aluminium induced by low-energy highly charged argon ions

Al K-shell X-ray yields are measured with highly charged Arq+ ions (q = 12-16) bombarding against aluminium. The energy range of the Ar ions is from 180 to 380 keV. K-shell ionization cross sections of aluminium are also obtained from the yields data. The experimental data is explained within the framework of 2p pi-2p sigma s rotational coupling. When Ar ions with 2p-shell vacancies are incident on aluminium, the vacancies begin to reduce. Meanwhile, collisions against Al atoms lead to the production of new 2p-shell vacancies of Ar ions. These Ar 2p-shell vacancies will transfer to the 1s orbit of an Al atom via 2p pi-2p sigma s rotational coupling leading to the emission of a K-shell X-ray of aluminiun. A model is constructed based on the base of the above physical scenario. The calculation results of the model are in agreement with the experimental results.

Average energy loss measured in single and double electron capture collisions of He2 on Ar at low velocities

Employing the recoil ion momentum spectroscopy we investigate the collision between He2+ and argon atoms. By measuring the recoil longitudinal momentum the energy losses of projectile are deduced for capture reaction channels. It is found that in most cases for single- and double-electron capture, the inner electron in the target atom is removed, the recoil ion is in singly or multiply excited states (hollow ion is formed), which indicates that electron correlation plays an important role in the process. The captured electrons prefer the ground states of the projectile. It is experimentally demonstrated that the average energy losses are directly related to charge transfer and electronic configuration.