Charge redistribution and phonon entropy of vanadium alloys

The effects of alloying on the lattice dynamics of vanadium were investigated using inelastic neutron scattering. Phonon densities of states were obtained for bcc solid solutions of V with 3d, 4d, and 5d transition metal solutes, from which vibrational entropies of alloying were obtained. A good correlation is found between the vibrational entropy of alloying and the electronegativity of transition metal solutes across the 3d row and down columns of the periodic table. First-principles calculations on supercells matching the experimental compositions predicted a systematic charge redistribution in the nearest-neighbor shell around the solute atoms, also following the Pauling and Watson electronegativity scales. The systematic stiffening of the phonons is interpreted in terms of the modified screening properties of the electron density around the solutes.     

Mechanical properties of polymer mixtures: Effect of compatibility

The effect of compatibility on the mechanical properties of polymer mixtures is discussed. From solution thermodynamics we conclude that for compatible mixtures of high molecular weight polymers the excess internal energy of mixing must be negative. For most polymer mixtures, this results in a negative excess volume of mixing. The excess entropy of mixing is therefore also negative. These general conclusions point to a stiffening of the solid lattice and a reduction in chain mobility. In dynamic mechanical behavior, the relaxation of molecular moieties responsible for the specific interaction should be shifted to intermediate temperatures, and the relaxation of other moieties should be shifted to higher temperatures if the potential well is inter-molecular. In finite deformation behavior craze initiation stress and shear yielding stress should both be higher than a linear combination of the properties of the pure components.     

The role of vibrations in thermodynamic properties of Cu-Ni alloys

We report results of a systematic study for vibrational thermodynamic functions of Cu-Ni alloys, in the harmonic approximation, using interaction potentials based on the embedded atom method with improved optimization techniques. The vibrational density of states of the systems is calculated using real space Green’s function method. From an investigation of local force fields we found that increasing Ni concentration in the alloy substantially stiffens the force experienced by Cu atoms compared to that of Ni atoms. Our calculations also reveal that vibrational entropy change between ordered and disordered crystals of Cu-Ni is negligible. However, the mixing entropy of the phonons and electronic states is found to be negative and favors un-mixing, and thus contributes to the miscibility gap.     

Vibrational entropy and the structural organization of proteins

In this paper we analyze the vibrational spectra of a large ensemble of non-homologous protein structures by means of a novel tool, that we coin Hierarchical Network Model (HNM). Our coarse-grained scheme accounts for the intrinsic heterogeneity of force constants displayed by protein arrangements and also incorporates side chain degrees of freedom. Our analysis shows that vibrational entropy per unit residue correlates with the content of secondary structure. Furthermore, we assess the individual contribution to vibrational entropy of the novel features of our scheme as compared with the predictions of state-of-the-art network models. This analysis highlights the importance of properly accounting for the intrinsic hierarchy in force strengths typical of the different atomic bonds that build up and stabilize protein scaffolds. Finally, we discuss possible implications of our findings in the context of protein aggregation phenomena.     

Theoretical insight of adsorption thermodynamics of multifunctional molecules on metal surfaces

Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries.     

Importance of solute–solute interactions on glass formability

Microalloying experiments on amorphous Al₈₄La₄Er₂Ni₈TM₂ alloys were performed with the substitution of all 3d TM (transition metal) elements and one 4d TM element. The critical thickness of the amorphous alloys was used as a criterion for glass formability in this system. The results show that, other than atomic size differences and the negative heats of mixing among the solvent and solute atoms, the atomic interactions among the solute atoms play an important role on glass formation. When the solute–solute interaction becomes repulsive (positive heat of mixing), glass formability suffers. Similarly, when the solute–solute interaction becomes highly attractive, exceeding that between the solvent and solute atoms, glass formability is also degraded. Evaluation of a large number of known multicomponent bulk metallic glasses provides additional support to these conjectures. This study shows that the solute–solute interaction plays an important role in glass formation, which has not been recognized previously.     

水在金属表面的氢键网络结构振动谱研究

用从头计算分子动力学模拟方法研究了水在Pt(111)表面上的吸附。总能优化和振动谱分析都表明，在这个表面上水以有序的分子态双层结构存在。这一结论和最近对水在Ru(0001)表面上吸附的计算结果相悖，但和已有的实验相符。此外，文章作者首次确定双层结构中存在两种不同的氢键形式。这两种氢键可以通过0H伸缩振动模的振动谱得到直接证实。     

Vibrational recognition of hydrogen-bonded water networks on a metal surface

The adsorption of water on Pt(111) surface has been studied with ab initio molecular dynamics simulation. Both the energetics and vibrational dynamics indicate the existence of a well-ordered molecular bilayer on this surface. This conclusion is in contrast to the recent result of water on Ru(0001) surface, but agrees with available experiments. In addition, our calculation identifies two different hydrogen bonds in the bilayer. Both can be directly recognized from the vibrational spectra of the OH stretch modes.     

Thermodynamic properties and ordering in liquid NaK alloys

The thermodynamic activities of sodium and potassium were determined by vapour-phase absorption spectrophotometry of atomic resonance lines. Both components exhibit significant positive deviations from ideality. Excess Gibbs energies computed from the activity data were combined with available heat-of-mixing data to yield values for excess entropies. The entropy of mixing which was found to be ideal in the sodium-rich liquid alloys provides no support for the earlier speculations about the existence of Na₂K molecules therein. The partial molar excess entropy of sodium in dilute solution in potassium was found to be surprisingly large and negative for a system of this type. A plausible model, involving sodium-sodium pairing, is proposed to account for the loss of configurational entropy.     

Large vibrational effects upon calculated phase boundaries in Al-Sc

The fcc portion of the Al-Sc phase diagram is calculated from first principles including contributions to alloy free energies associated with ionic vibrations. It is found that vibrational entropy accounts for a 27-fold increase in the calculated solubility limits for Sc in fcc Al at high temperatures, bringing calculated and measured values into very good agreement. The present work gives a clear example demonstrating a large effect of vibrational entropy upon calculated phase boundaries in substitutional alloys.     

Structural relationship between negative thermal expansion and quartic anharmonicity of cubic ScF3

Cubic scandium trifluoride (ScF3) has a large negative thermal expansion over a wide range of temperatures. Inelastic neutron scattering experiments were performed to study the temperature dependence of the lattice dynamics of ScF3 from 7 to 750 K. The measured phonon densities of states show a large anharmonic contribution with a thermal stiffening of modes around 25 meV. Phonon calculations with first-principles methods identified the individual modes in the densities of states, and frozen phonon calculations showed that some of the modes with motions of F atoms transverse to their bond direction behave as quantum quartic oscillators. The quartic potential originates from harmonic interatomic forces in the DO9 structure of ScF3, and accounts for phonon stiffening with the temperature and a significant part of the negative thermal expansion.     

X-ray absorption analysis of sputter-grown Co/Pt stackings before and after helium irradiation

We have studied the local order around cobalt atoms in Pt/Co/Pt layered systems gradually modified by irradiation using 30 keV helium ions. Using X-ray diffraction and X-ray Absorption Fine Structure, we have determined the crystallographic order, the number of Co-Co and Co-Pt bonds and the corresponding bond lengths both in-plane and in the perpendicular direction. The comparison with an interdiffusion model highlights the unexpected complexity of the initial Pt/Co/Pt nanostructure. We use the Néel/Bruno model of magnetic anisotropy to correlate the structure and the magnetic hysteresis properties. We then identify the structural consequences of irradiation onto the short range order. The irradiation induces a substitutional mixing maintaining the initial crystallographic structure. We confirm that the mixing rate is in agreement with a ballistic mechanism of mixing. In addition, we show that the previously reported irradiation-induced controlled decrease of the magnetic anisotropy can not be solely attributed to Co-Pt intermixing: irradiation also significantly releases the 3.4% tensile strain of the cobalt-rich dense planes. We finally speculate on the class of magnetic materials the concept of light ion irradiation could be extended to.     

低密度溶液中溶剂的重组织性质

分析了溶液的微观结构 ,结果表明 ,单个溶质粒子影响其周围的溶剂的结构 ,溶质粒子间的相互作用也将影响溶剂的结构 ,溶质对溶剂结构的影响称作溶剂的重组织 .提出了二阶重组织能及二阶重组织熵等概念 ,可以描述在两个溶质粒子发生碰撞时对其周围溶剂结构的影响 .利用二元系的集团展开理论 ,给出了溶剂的一阶、二阶重组织能和重组织熵的表达式 .统计热力学分析给出了溶剂 溶剂径向分布函数与溶质和溶剂化学势之间的关系 ,给出了无限稀溶液模型是否成立的宏观判据 .提出的理论可用于低密度的二元溶液 .     

Investigation of molecular dynamics in β-carotene using femtosecond pump-FWM spectroscopy

We have carried out two different pump four-wave mixing experiments, combining an initial pump excitation and a subsequent four-wave mixing probe process, on the photosynthetic pigment β-carotene to reveal different aspects of its molecular dynamics after photoexcitation. Firstly, the pump degenerate four-wave mixing (pump -DFWM) technique, in which the DFWM is resonant with the S₁- to S _n -transition of β-carotene, is used to monitor the events following excitation of the system. The transient shows a peculiar shape and is seen to depend on the energy of the initial pump pulse as well as on the concentration of the solute in the solvent. Secondly, pump coherent anti-Stokes Raman scattering (pump-CARS) is used to elucidate the excited state vibrational dynamics of β-carotene. This technique gives access to the dynamics of both ground and excited electronic states with vibrational selectivity.     

Microscopic theory of intrinsic shear and bulk viscosities

A microscopic theory of intrinsic shear and bulk viscosities of solutions is given for a model of particles that interact with hard-sphere cores and weak longrange attraction. The approximation considered (the velocity chaos assumption of the Enskog theory) can be expected to yield quantitatively useful values for viscosities of the model solute-solvent system when the solute particles are not much larger than the solvent particles. Under solute-solvent mixing conditions of constant pressure and temperature we find that the intrinsic viscosities of a hard-sphere solute in a hard-sphere solvent can be positive or negative, depending upon size and mass ratios; for solute and solvent particles whose mass ratio equals their volume ratio, the intrinsic shear and bulk viscosities are always positive for solute particles larger than solvent particles: in the opposite case, the intrinsic shear viscosity is always negative while the intrinsic bulk viscosity is for the most part negative, becoming positive again when the solute particle is sufficiently small. For solute particles smaller than solvent particles, this result is sensitive to change in mass ratio. The addition of solvent-solvent attraction is found to lower the intrinsic viscosities substantially; the addition of solute-solvent attraction raises it. Detailed quantitative analysis of these effects is given.     

Binding enthalpies and entropies of neutral Zn,In And Sn In Ge

A statistical thermodynamical model is developed for a doubly ionizable acceptor with excited states in an elemental semiconductor. The special cases of a singly ionizable acceptor, no excited acceptor states and a neutral solute are readily extracted. The equations obtained describe not only the distribution of an acceptor among its various electronic states but also the chemical potentials of the acceptor atom and of the solvent atom. The equations are applied, with and without the excited states included, to obtain about equally good fits to the low-temperature, low carrier concentration Hall data for Zn in Ge. For the low impurity concentrations involved, the excited states are present and so should be included in the analysis. The ability to obtain an equally good fit with the excited states omitted is most likely due to the fact that the concentrations of the major Zn impurity and the Sb counter dopant are not fixed independently of the Hall measurements. The additional flexibility obtained by treating these concentrations as adjustable parameters is sufficient to compensate for the error made in neglecting the excited states. In contrast, the solubilities of the acceptors Zn and In are large enough that the excited states should be pushed out of the band gap. Consequently, the equations are applied without the excited states to the experimental chemical potential-solubility data for Zn, In and Sn in Ge to obtain the Gibbs energy, enthalpy and entropy of binding for the neutral (un-ionized) solute at 950 K. With a solute reference phase consisting of an ideal monatomic gas at 0 K, the entropy of binding is close to that for Ge itself, $\text{14.6 cal}\text{K g}$ atom. This implies that, when they are in the neutral state, these substitutional solute atoms behave very much like the Ge atom itself in contributing to the vibrational spectrum. However, the enthalpy of binding varies significantly and is ?3.8, ?39 and ?65 $\text{kcal}\text{g}$ atom for neutral Zn, neutral In and Sn, respectively, compared to $\text{?84 kcal}\text{g}$ atom for Ge.     

Thermal loss mechanism in the generation of multifrequency laser emission via stimulated Raman scattering and four-wave Raman mixing studied by photothermal refraction spectroscopy

The heat produced in conjunction with the processes of stimulated Raman scattering and four-wave Raman mixing in hydrogen was measured by photothermal refraction spectroscopy. Many vibrational, rotational, and vibrationally shifted rotational Raman lines are exclusively/simultaneously generated by changing the polarization of the laser beam and the hydrogen pressure. Thermal loss occurs predominantly from vibrational Raman scattering, which can be ascribed to a large Raman shift frequency of 4155 cm^-1 for the vibrational transition. In contrast to stimulated Raman scattering, little or no thermal loss is observable during the process of four-wave Raman mixing. Received: 12 April 1999 / Revised version: 12 July 1999 / Published online: 20 October 1999     

Effect of neon mixing on vibrational temperature of molecular nitrogen plasma generated at 13.56 MHz

Optical emission spectroscopy is used to investigate the effect of neon mixing on the electron temperature and vibrational temperature of second positive and first negative system of nitrogen plasma generated by 13.56 MHZ RF generator. The electron temperature is determined from NeI lines intensities, using Boltzman's plot. The relative changes in vibrational population of N₂(C³Πu) and states with neon mixing are monitored by measuring the emission intensities of second positive and first negative system of nitrogen molecules. Vibrational temperature is calculated for the sequences Δν=0,1,−2, that follows the Boltzman's distribution. It is found that electron temperature as well as vibrational temperature of second positive and first negative system can be raised significantly by mixing neon in nitrogen plasma. Vibrational temperature at 250 watt RF power, of second positive system is raised up to 0.67 eV at 90% neon where as for first negative system it is raised up to 0.78 eV. It is found that vibrational temperature increases with the gas pressure.     

Collective vibrational modes in strong electrolyte solutions at high concentrations

We report evidence for the existence of solute related collective vibrational modes in strong II-I electrolyte solutions at high concentrations both in H₂O and D₂O. The evidence was obtained by studying the polarized Raman spectra of solutions of CdCl₂ and NiCl₂ Checks were also performed by taking the Raman spectra of the relative hydrated salts. Our results are explained in terms of vibrational densities of states corresponding to collective vibrational modes in a solute connected middle range lattice.