A detailed investigation on the global minimum structures of mixed rare‐gas clusters: Geometry,energetics, and site occupancy

We performed a global minimum search of mixed rare‐gas clusters by applying an evolutionary algorithm (EA), which was recently proposed for binary atomic systems (Marques and Pereira, Chem. Phys. Lett. 2010, 485, 211). Before being applied to the potentials used in this work, the EA was further tested against results previously reported for the Ar_NXe_38?N clusters and several new putative global minima were discovered. We employed either simple Lennard‐Jones (LJ) potentials or more realistic functions to describe pair interactions in Ar_NKr_38?N, Ar_NXe_38?N, and Kr_NXe_38?N clusters. The long‐range tail of the pair‐potentials shows some influence on the energetic features and shape of the structure of clusters. In turn, core–shell type structures are mostly observed for global minima of the binary rare‐gas clusters, for both accurate and LJ potentials. However, the long‐range tail of the potential may have influence on the type of atoms that segregate on the surface or form the core of the cluster. While relevant differences for the preferential site occupancy occur between the two potentials for Ar_NKr_38?N (for N > 21), the type of atoms that segregate on the surface for Ar_NXe_38?N and Kr_NXe_38?N clusters is unaffected by the accuracy of the long‐range part of the interaction in almost all cases. Moreover, the global minimum search for model‐potentials in binary systems reveals that the surface‐site occupancy is mainly determined by the combination of two parameters: the size ratio of the two types of particles forming the cluster and the minimum‐energy ratio corresponding to the pair‐interactions between unlike atoms. © 2012 Wiley Periodicals, Inc.     

An unusual partial occupancy of labile chloride and aqua ligands in cocrystallized isomers of a nickel(II) complex bearing a tripodal N4‐donor ligand

A novel Ni²⁺ complex with the N₄‐donor tripodal ligand bis[(1‐methyl‐1H‐imidazol‐2‐yl)methyl][2‐(pyridin‐2‐yl)ethyl]amine (L), namely, aqua{bis[(1‐methyl‐1H‐imidazol‐2‐yl‐κN³)methyl][2‐(pyridin‐2‐yl‐κN)ethyl]amine‐κN}chloridonickel(II) perchlorate, [NiCl(C₁₇H₂₂N₆)(H₂O)]ClO₄ or [NiCl(H₂O)(L)Cl]ClO₄ ( 1 ), was synthesized and characterized by spectroscopic and spectrometric methods. The crystal structure of 1 reveals an interesting and unusual cocrystallization of isomeric complexes, which are crystallographically disordered with partial occupancy of the labile cis aqua and chloride ligands. The Ni²⁺ centre exhibits a distorted octahedral environment, with similar bond lengths for the two Ni—N(imidazole) bonds. The bond length increases for Ni—N(pyridine) and Ni—N(amine), which is in agreement with literature examples. The bond lengths of the disordered labile sites are also in the expected range and the Ni—Cl and Ni—O bond lengths are comparable with similar compounds. The electronic, redox and solution stability behaviour of 1 were also evaluated, and the data obtained suggest the maintenance of structural integrity, with no sign of demetalation or decomposition under the studied conditions.     

Tree approximation of the long wave radiation parameterization in the NCAR CAM global climate model

The computation of Global Climate Models (GCMs) presents significant numerical challenges. This paper presents new algorithms based on sparse occupancy trees for learning and emulating the long wave radiation parameterization in the NCAR CAM climate model. This emulation occupies by far the most significant portion of the computational time in the implementation of the model. From the mathematical point of view this parameterization can be considered as a mapping R²²⁰→R³³ which is to be learned from scattered data samples (xⁱ,yⁱ), i=1,…,N. Hence, the problem represents a typical application of high-dimensional statistical learning. The goal is to develop learning schemes that are not only accurate and reliable but also computationally efficient and capable of adapting to time-varying environmental states. The algorithms developed in this paper are compared with other approaches such as neural networks, nearest neighbor methods, and regression trees as to how these various goals are met.     

Statistical Mechanics and Thermodynamics: Boltzmann’s versus Planck’s State Definitions and Counting

During the physical foundation of his radiation formula in his December 1900 talk and subsequent 1901 article, Planck refers to Boltzmann’s 1877 combinatorial-probabilistic treatment and obtains his quantum distribution function, while Boltzmann did not. For this, Boltzmann’s memoirs are usually ascribed to classical statistical mechanics. Agreeing with Bach, it is shown that Boltzmann’s 1868 and 1877 calculations can lead to a Planckian distribution function, where those of 1868 are even closer to Planck than that of 1877. Boltzmann’s and Planck’s calculations are compared based on Bach’s three-level scheme ‘configuration–occupation–occupancy’. Special attention is paid to the concepts of interchangeability and the indistinguishability of particles and states. In contrast to Bach, the level of exposition is most elementary. I hope to make Boltzmann’s work better known in English and to remove misunderstandings in the literature.     

Percolation of dimers on square lattices

A theoretical approach, based on exact calculations of configurations on finite rectangular cells, is applied to study the percolation of homonuclear dimers on square lattices. An efficient algorithm allows us to calculate the detailed structure of the configuration space for M=_Lx×_Ly$M=L_x\times L_y$ cells, with M$M$ varying from 16 to 36. The percolation process has been monitored by following the percolation function, defined as the ratio between the number of percolating configurations and the total number of available configurations for a given cell size and concentration of occupied sites. The percolation threshold has been calculated by means of two complementary methods: one based on well-known renormalization techniques and the other based on determining the inflection point of the percolation function curves. A comparison of the results obtained by these two methods has been performed. The study includes the use of finite-size scaling theory to extrapolate numerical results towards the thermodynamic limit. The effect of jamming due to dimers is also established. Finally, the critical exponents ν$\nu$, β$\beta$ and γ$\gamma$ have been obtained and values compared with numerical results and expected theoretical estimations. The present results show agreement and even improvement (in the case of γ$\gamma$) with respect to some numeric values available in the literature.     

CO_2—CH_4—N_2瓦斯混合气水合分离产物Raman光谱特征

抽采瓦斯气分离产物特性精确获取是水合分离新技术应用关键。针对两种浓度构成的瓦斯混合气(CO2—CH4—N2),利用瓦斯水合分离产物Raman测试装置,原位合成两种水合物样品并观测Raman光谱。基于客体分子振动模式、"松笼-紧笼"模型及Raman谱带面积比,结合van der Waals-Platteeuw模型,确定出水合物晶体结构,计算出晶体孔穴占有率、水合指数等结构参数。结果表明,两种瓦斯水合物样品均为Ⅰ型结构,其大孔穴占有率分别为98.57%和98.52%,小孔穴占有率分别为29.93%和33.87%,小孔穴不易被客体分子填充;两种分离产物水合指数比较接近,分别为7.14和6.98,均大于Ⅰ型水合物水合指数理论值。     

Quantitative determination of anti-structured defects applied to alloys of a wide chemical range

Anti-structured defects bridge atom migration among heterogeneous sublattices facilitating diffusion but could also result in the collapse of ordered structure.Component distribution Ni_(75)Al_xV_(25-x) alloys are investigated using a microscopic phase field model to illuminate relations between anti-structured defects and composition,precipitate order,precipitate type,and phase stability.The Ni_(75)Al_xV_(25-x) alloys undergo single Ni_3V(stage Ⅰ),dual Ni_3Al and Ni_3V(stage Ⅱ with Ni_3V prior;and stage Ⅲ with Ni_3Al prior),and single Ni_3Al(stage Ⅳ) with enhanced aluminum level.For Ni_3V phase,anti-structured defects(V_(Ni1),Niy,except V_(Ni2)) and substitution defects(Al_(Ni1),Al_(Ni2),Al_v) exhibit a positive correlation to aluminum in stage I,the positive trend becomes to negative correlation or smooth during stage Ⅱ.For Ni_3 Al phase,anti-structured defects(Al_(Ni),Ni_(Al)) and substitution defects(V_(Ni),V_(Al)) have a positive correlation to aluminum in stage Ⅱ,but Ni_(Al) goes down since stage Ⅲ and lasts to stage Ⅳ.V_(Ni) and V_(Al) fluctuate when Ni_3Al precipitates prior,but go down drastically in stageⅣ.Precipitate type conversion of single Ni_3V/dual(Ni_3V+Ni_3Al) affects Ni_3V defects,while dual(Ni_3V+Ni_3Al)/single Ni_3 Al has little effect on Ni_3Al defects.Precipitate order swap occurred in the dual phase region affects on Ni_3Al defects but not on Ni_3V.     

Competitive cage occupancy of hydrogen and argon in structure-II hydrates

The cage occupancy of hydrogen in the single-crystals of simple hydrogen hydrates and hydrogen + argon mixed-gas hydrates was investigated by means of in situ Raman spectroscopy under the three-phase (hydrate + water + fluid) equilibrium condition. In the equilibrium pressure region higher than approximately 25 MPa, four hydrogen cluster and argon competitively occupied the large cages of structure-II hydrogen + argon mixed-gas hydrates. In addition, Raman spectroscopic analysis at liquid nitrogen temperature (77 K) supports that the clusters of two, three, or four hydrogen molecules occupy large cages.