Negative heat capacity of Ar55 cluster

The solid–liquid phase transitions of Ar₅₅ cluster was simulated by the microcanonical molecular dynamics and microcanonical parallel tempering methods using Lennard–Jones potential, and thermodynamic quantities were calculated. The caloric curve of cluster has S-bend. To understand this behaviour, configurational and total entropies were evaluated, and the dents on the entropy curves were noticed as the sign of negative heat capacity. The heat capacities were evaluated by using configurational entropy data. The potential energy distributions have bimodal behaviour in the given range at the melting temperature. At the same time by using configurational entropy canonical caloric curve and canonical heat capacity were calculated. To obtain entropy change upon melting, total entropy were calculated from the caloric curve. The microcanonical results melting temperature, latent heat and entropy change upon melting values were reported and compared with the values reported in the literature and the values calculated from the thermodynamic relations offered for bulk matter, consistent values were found.     

A statistical theory of orientational ordering at the free surface of a liquid of ellipsoidal molecules

The surface tension γ of a system of ellipsoidal molecules is evaluated approximately using a generalized Fowler-Kirkwood-Buff model. The pair potential is modelled as u(r/σ) where r is the centre of mass distance and σ is an angle dependent range parameter determined by the shape anisotropy of the molecule. It is shown that if the pair correlation function g scales as g(r/σ) γ can be mapped onto the value for a system of spheres, multiplied by an angular integral which takes into account approximately both the anisotropic molecular shape as well as possible orientational order. It is shown that γ is lowered when the orientational order parameter Q ≠ 0, implying that isotropic molecular liquids may be partially ordered near the free surface. The surface favours parallel ordering of rod-like particles in a direction in the plane of the surface. For plate-like particles, ordering with the plates in the plane of the surface is favoured. In both cases the anchoring energies increase sharply with the shape anisotropy of the molecule. These results are qualitatively consistent with the surface properties of non-polar nematic liquid crystals.     

Peculiar thermodynamic properties of LJ<Subscript> N</Subscript> (N = 39–55) clusters

The solid-liquid phase transitions of Lennard-Jones clusters LJ_N (N=39–55) were simulated by a microcanonical molecular dynamics method using Lennard-Jones potential, and their thermodynamic quantities were calculated. The caloric curves of clusters (except N=42) have S-bend. To understand this behaviour, configurational and total entropies were evaluated, and dents on the entropy curves were taken as a sign of negative heat capacity. The heat capacities were evaluated for N=39–55 clusters using configurational entropy data. The potential energy distributions have bimodal behaviour for all clusters in the given range at the melting temperature. The distinct melting behaviour of LJ₄₂ was explained by the topology of the potential energy surface by examining the isomer distributions at phase transitions for LJ₃₉-LJ₅₅. The isomer distributions were found to be a useful way to interpret this behaviour and melting dynamics in general. Melting temperature, latent heat and entropy change upon melting values were reported and are consistent with literature values and values calculated from bulk thermodynamic properties. The dependence of these quantities on the size of the clusters was examined and it is found that latent heat is the key quantity to determine the magic numbers.     

First-principles study of dissociation processes of O2 molecular on the Al (111) surface

The trajectories of adsorption and dissociation process of O₂ on the Al (111) surface were studied by the spin-polarized ab initio molecular dynamics method, and the adsorption activation energy was clarified by the NEB method with hybrid functionals. Three typical dissociation trajectories were found through simulation of O₂ molecule at different initial positions. When vertically approaches to the Al surface, the O₂ molecule tends to rotate, and the activation energy is 0.66eV. If O₂ molecule does not rotate, the activation energy will increase to 1.43 eV, and it makes the O atom enter the Al sublayer eventually. When the O₂ molecules parallel approach to the Al surface, there is no activation energy, due to the huge energy released during the adsorption process.     

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.     

The Adam–Gibbs relation and the TIP4P/2005 model of water

ABSTRACT

We report a numerical test of the Adam–Gibbs relation for the TIP4P/2005 model of water. The configurational entropy is here evaluated as the logarithm of the number of different basins in the potential energy landscape sampled in equilibrium conditions. Despite the non-monotonic behaviour which characterise the density dependence of the diffusion coefficient, the Adam–Gibbs relation is satisfied within the numerical precision in a wide range of densities and temperatures. We also show that expressions based on the excess entropy (the logarithm of the number of sampled microstates in phase space) fail in the region of densities where a tetrahedral hydrogen bond network develops.     

Generalization of the Williams--Landel--Ferry equation

Based on the model of Gibbs-Di Marzio we write the logarithmic shift factor without explicit knowledge of the form for the entropy, an expression which enables us to write a generalization of the Williams--Landel--Ferry equation. Comparison with the empirical relation of Williams--Landel--Ferry and use of the fact that the model exhibits the existence of a isoentropic temperature T₀ for which the configurational entropy of the system vanishes, leads to a value of the isoentropic temperature for which the configurational entropy of the system vanishes. The form for the specific heat proposed by Dowell and Di Marzio based on the lattice model of Gibbs-Di Marzio for the glass transition of polymeric substances, has been used by García-Colín et al. to find the molar configurational entropy (MCE) of glass. Knowledge of the form of the MCE, allows us to find an expression for the critical configurational entropy (S^*_c) and a form for the potential energy hindering the cooperative rearrangement per monomer segment (Δμ).     

Mechanism of H2S molecule adsorption on the GaAs(100) surface: Ab initio quantum-chemical analysis

Ab initio quantum-chemical cluster calculations within the density-functional theory were carried out to study the mechanism of H₂S molecule adsorption on the gallium-rich surface of GaAs(100). It was shown that adsorption can occur in four stages: molecular adsorption; dissociative adsorption, during which an HS radical is adsorbed on a gallium atom comprising a dimer while the detached hydrogen atom is adsorbed on another surface atom of the semiconductor; hydrogen adatom migration between neighboring surface atoms of the semiconductor; and the formation of a Ga-S-Ga bridge bond and of a hydrogen molecule. The stationary-state energies and energy barriers to transitions between these states were determined. The conclusions drawn based on an analysis of calculated diagrams of the potential energy of the processes that occur are in good agreement with the experimental data available in the literature.     

In search of the Griffiths shield region

The van der Waals equation of state for binary mixtures has been used to determine the location and shape of the Griffiths shield region (where three tricritical lines intersect). If one takes the geometric mean fora ₁₂, the arithmetic mean forb ₁₂, and the configurational free energy as ideal, the center of the Griffiths shield region is found only when the ratio of molecular sizes is infinite. When the Flory equation for the configurational free energy for mixtures of chain molecules is substituted for the ideal form, the results appear to be somewhat different. However, for all the cases studied, with systems which approach geometric mean behavior one finds the shield region only when the ratio of molecular size is very large and when the internal pressure of the small molecule is very much greater than that of the long-chain molecule.This paper is dedicated to our colleague Howard Reiss on the occasion of his 66th birthday.     

PdCO分子结构与势能函数

用密度泛函理论的B3LYP方法,对钯原子采用LANL2DZ收缩价基函数,碳原子和氧原子采用AUG-cc-pVTZ基组,对PdC,PdO和PdCO体系的结构进行优化,计算表明：PdC分子基态为¹Σ⁺态,键长为R_e=0.17285nm,离解能为4.919eV.PdO分子基态的平衡核间距为0.18546nm,其电子态为³Π,离解能为2.455eV,并拟合得到Murrell-Sorbie势能函数;PdCO分子有两 关键词： PdCO 分子结构 势能函数     

Simulation study of argon adsorption on (0 0 1) faces of phyllosilicates

Grand Canonical Monte Carlo molecular simulations have been performed for argon and nitrogen adsorption on the basal surfaces of phyllosilicates without surface cations. The results have been compared with derivative isotherms analysis of experimental data. An optimization of the surface-Ar interaction has been performed by varying the oxygen atom LJ ?/k_B parameter and the optimized value was used to perform the nitrogen adsorption simulations. The analysis of the argon adsorption simulation indicates that adsorption mechanisms are more complex than may be suggested by experimental results obtained by low-pressure adsorption. The structure of the adsorbed film has a marked dynamic behaviour and the monolayer capacity strongly depends on the equilibrium relative pressure. For nitrogen adsorption, while high pressure behaviour is simulated adequately, some deviation is observed in low-pressure region of the isotherms suggesting that additional simulation and perhaps the use of a more sophisticated potential to model the nitrogen molecule can be necessary to understand fully the behavior of this gas on clay minerals.     

Equilibrium adsorption of water-like molecules on single nanospheres

Water-like gas adsorption on spherical nano-aerosol particles has been studied for particles of different sizes at different temperatures with density functional theory. The water-like fluid was modelled as Lennard–Jones (LJ) spheres with four hydrogen-bonding sites with parameters adjusted to the phase diagram of water. For the single sphere case, both the adsorption excesses and density profiles approach those of the plane cases as the spherical substrate sizes increase; at each temperature studied, the size dependence of the transition from thin-film adsorption to thick-film adsorption has been observed. What we found here support earlier suggestions (J. X. Fang, W. H. Marlow, J. X. Lu, and R. R. Lucchese, J. Chem. Phys. 107, 5212 (1997)) that not only the interaction energies between the water molecule and the spherical substrate are sensitive to the size of the spherical substrate, but also the wetting behaviour. In calculations of the excess adsorptions of particles of radii R?=?20σ, 30σ, and 50σ, these substrates show the expected transition from the single molecule to the macroscopic aerosol particles.     

A simple route to the energy shift between an electrically polarizable molecule and a magnetically susceptible molecule via the electromagnetic energy density

The van der Waals dispersion interaction between a molecule that is electrically polarizable and one that is magnetically susceptible, is recalculated within the framework of non-relativistic quantum electrodynamics. The energy shift is obtained in a simple way by calculating the response of a test polarizable body to the electromagnetic energy density due to a second source molecule. It is confirmed that the near-zone asymptote of the potential between an electric dipole polarizable molecule and a paramagnetic one varies as R ^{? 4}. Inclusion of the often neglected diamagnetic coupling term, however, results in an R ^?5 dependent short-range behaviour, which is seen to dominate over the paramagnetic contribution in the near-zone. For larger intermolecular distances, the expected R ^?7 dependence on separation is found for both paramagnetic and diamagnetic susceptible molecules interacting with an electric dipole polarizable one.     

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.     

Quantum entanglement in elliptical quantum corrals

Quantum corrals present interesting properties due to the combination of confinement and, in the case of elliptical corrals, to their focalizing properties. We study the case when two magnetic impurities are added to the non-interacting corral, where they interact via a superexchange AF interaction J with the surface electrons in the ellipse. Previous results showed that, when both impurities are located at the foci of the system, they experience an enhanced magnetic interaction, as compared to the one they would have in an open surface. For small J and even filling, they are locked in a singlet state, which weakens for larger values of this parameter. When J is much larger than the hopping parameter of the electrons in the ellipse, both spins decorrelate while forming a local singlet with the electrons of the ellipse, thus presenting a confined RKKY–Kondo transition.We interpret this behaviour by means of the von Neumann entropy between the localized impurities and the itinerant electrons of the ellipse: for small J the entropy is nearly zero while for large J it is maximum. In addition, the local density of states provides us with a concrete experimental tool for detecting the Kondo regime.     

Adsorption of hydrogen in defective carbon nanotube: modelling and consequent investigations using statistical physics formalism

ABSTRACT

Experimental adsorption isotherms of hydrogen in CNT samples (CNT-A, activated CNT-A CNT-B and activated CNT-B) at T?=?77, 87 and 90?K have been fitted using some theoretical model expressions treated by statistical physics through the grand canonical ensemble. The monolayer model with single energy is selected to fit and interpret the experimental data obtained with CNTs. The physico-chemical parameters, interfering in the adsorption process and implicated in the model expressions, could be directly determined from the experimental data through numerical simulation. Three parameters of the model are fitted, namely the number of hydrogen molecule per site n, the interstitial site density N_m and the energetic parameter P_1/2. The evolution of these parameters as function of temperature is plotted and interpreted in relation to adsorption process. Finally, the thermo-dynamic potential functions, which involve in the adsorption mechanism like free enthalpy of Gibbs G_a, internal energy E_int and entropy S_a, are derived by statistical physics calculations from the selected model.     

The structure and the potential energy function of AlSO(C_S,X~2A″)

By using the B3P86/aug-cc-pvtz method,the accurate equilibrium geometry of the AlSO(CS,X2A″) molecule has been calculated and compared with available theoretical values.The obtained results show that the AlSO molecule has a most stable structure with bond lengths of R OAl = 0.1864 nm,R OS = 0.1623 nm,R AlS = 0.2450 nm,together with a dissociation energy of 13.88 eV.The possible electronic states and their reasonable dissociation limits for the ground state of the AlSO molecule were determined based on the principle of atomic and molecular reaction statics.The analytic potential energy function of the AlSO molecule was derived by the many-body expansion theory and the contour lines were constructed for the first time,which show the internal information of the AlSO molecule,including the equilibrium structure and stable point.The analysis demonstrates that the obtained potential energy function of AlSO is reasonable and successful and the present investigations provide important insights for further study on molecular reaction dynamics.     

Molecular hydrogen and oxygen interactions with armchair Si nanotubes

Molecular hydrogen and oxygen adsorptions on a (6, 6) armchair silicon nanotube have been studied by optimizing the distances of the admolecules from both inside and outside the tube. Full geometry and spin optimizations have been performed without any symmetry constraints with an all electron 3-21G* basis set and the B3LYP functional. The molecule is originally placed perpendicular or parallel to the tube axis. Hydrogen adsorption with the molecular axis aligned parallel to the surface of the nanotube is less favorable. Hydrogen molecule does not dissociate while oxygen molecule dissociates after optimization. The on-top site is the only preferred site for hydrogen molecule with an adsorption energy of 3.71 eV and an optimized distance of 3.31 for external adsorption whereas the on-top site is the most preferred site with adsorption energy of 3.69 eV for internal adsorption. For oxygen, the molecule dissociates and the most preferred sites are the two bridge sites with an adsorption energy of 9.64 eV, the optimized distance being 1.65/1.68 Å when it is adsorbed from the outside of the tube. When oxygen molecule is originally placed at on-top site it will hold as a molecule after adsorption with a slightly increased bond length. For the internal adsorption of oxygen, the molecules also dissociate in most cases and the zigzag bridge site is the most preferred site. After molecular adsorption for both hydrogen and oxygen, the buckling of the nanotubes increased. Frustration effects in the nanotube due to molecular adsorption are also noted.     

Coverage effects on phenol adsorption on Si(1 0 0)2 × 1 as: A first principle calculation

We investigated the adsorption of a 6-dimers Si(1 0 0)2 × 1 surface as a function of coverage and adsorption type (molecular/dissociative) by first principle calculations. In particular, we performed calculations on models with 2, 3, 4 and 6 phenol molecules, corresponding to coverage Θ = 0.34, 0.5, 0.67 and 1. We found that total adsorption energy, when at least one phenol is in a molecular state is lower than the sum of the corresponding singly adsorbed molecules. The dissociative adsorption of multiple molecules, both in parallel and switched configuration is most favoured for a coverage Θ = 0.34 (2.6 eV per adsorbed molecule). This values decreases to 2.0 eV and remains constant till the coverage 1 is reached.The energy barrier for the molecular-to-dissociated transition of a phenol molecule, in presence of another dissociatively adsorbed molecule is ∼0.008 eV and it is similar to the value in case of single adsorption. Possible hydrogen displacements were also considered.     

Adsorption of oxygen molecular on pristine and defected SiC nanotubes

The structural and electronic properties of oxygen molecular adsorbed on the exterior surface of pristine and N_C or B_C defected (10,0) or (6,6) SiCNT have been investigated systematically using the first-principles projector-augmented wave potential within the density-functional theory under the generalized-gradient approximation. We find that for both pristine tubes the preferred adsorption sites of the O₂ molecule are above and nearly parallel to armchair Si-C bond whether physisorption or chemisorption. The strong chemical interaction between O₂ molecule and tube leads to not only a vanishing in magnetism of the O₂ molecule but also an outward relaxation of the underlying Si-C bond. The C atom substituted by N or B atom assists O₂ molecule adsorption above and nearly parallel to zigzag Si-N or Si-B bond as well as imparts a metallic character on the SiCNTs with higher concentration of the defects or a magnetism on the SiCNTs with lower concentration of the defects. Therefore, a combination of N or B doping followed by exposure to air may be an effective way to tune the electronic properties of the semiconducting SiCNTs. Furthermore, the lower binding energies for the pair of oxygen interstitials chemisorbed on N_C or B_C defected (10,0) or (6,6) SiCNT show that the oxygen molecule will dissociate to the pair of oxygen interstitials at the sidewall of N_C or B_C defected SiCNTs.