Low-temperature Amorphous Phases Research Articles

Characterization of void space, large-scale structure, and transport properties of maximally random jammed packings of superballs

Dense, disordered packings of particles are useful models of low-temperature amorphous phases of matter, biological systems, granular media, and colloidal systems. The study of dense packings of nonspherical particles enables one to ascertain how rotational degrees of freedom affect packing behavior. Here, we study superballs, a large family of deformations of the sphere, defined in three dimensions by $|{x}_{1}{|}^{2p}+|{x}_{2}{|}^{2p}+{|{x}_{3}|}^{2p}\ensuremath{\le}1$, where $p\ensuremath{\in}(0,\ensuremath{\infty})$ is a deformation parameter indicating to what extent the shape deviates from a sphere. As $p$ increases from the sphere point ($p=1$), the superball tends to a cuboidal shape and approaches a cube in the $p\ensuremath{\rightarrow}\ensuremath{\infty}$ limit. As $p\ensuremath{\rightarrow}0.5$, it approaches an octahedron, becomes a concave body with octahedral symmetry for $p<0.5$, and approaches a three-dimensional cross in the limit $p\ensuremath{\rightarrow}0$. Previous characterization of superball packings has shown that they have a maximally random jammed (MRJ) state, whose properties (e.g., packing fraction $\ensuremath{\phi}$, average contact number $\overline{Z}$) vary nonanalytically as $p$ diverges from unity. Here, we use an event-driven molecular dynamics algorithm to produce MRJ superball packings with $0.85\ensuremath{\le}p\ensuremath{\le}1.50$. To supplement the previous work on such packings, we characterize their large-scale structure by examining the behaviors of their structure factors $S(Q)$ and spectral densities ${\stackrel{\ifmmode \tilde{}\else \~{}\fi{}}{\ensuremath{\chi}}}_{{}_{V}}(Q)$, as the wave number $Q$ tends to zero, and find that these packings are effectively hyperuniform for all values of $p$ examined. We show that the mean width $\overline{w}$ is a useful length scale to make distances dimensionless in order to compare systematically superballs of different shape. Moreover, we compute the complementary cumulative pore-size distribution $F(\ensuremath{\delta})$ and find that the pore sizes tend to decrease as $|1\ensuremath{-}p|$ increases. From $F(\ensuremath{\delta})$, we estimate how the fluid permeability, mean survival time, and principal diffusion relaxation time vary as a function of $p$. Additionally, we compute the diffusion ``spreadability'' $\mathcal{S}(t)$ [Torquato, Phys. Rev. E 104, 054102 (2021)] of these packings and find that the long-time power-law scaling indicates these packings are hyperuniform with a small-$Q$ power law scaling of the spectral density ${\stackrel{\ifmmode \tilde{}\else \~{}\fi{}}{\ensuremath{\chi}}}_{{}_{V}}(Q)\ensuremath{\sim}{Q}^{\ensuremath{\alpha}}$ with an exponent $\ensuremath{\alpha}$ that ranges from 0.64 at the sphere point to 0.32 at $p=1.50$, and decreases as $|1\ensuremath{-}p|$ increases. Each of the structural characteristics computed here exhibits an extremum at the sphere point and varies nonanalytically as $p$ departs the sphere point. We find the nonanalytic behavior in $\ensuremath{\phi}$ on either side of the sphere point is nearly linear, and determine that the rattler fraction ${\ensuremath{\phi}}_{R}$ decreases rapidly as $|1\ensuremath{-}p|$ increases. Our results can be used to help inform the design of colloidal or granular materials with targeted densities and transport properties.

Synthesis, structural and conformational analysis, and IR spectra of ethyl 4-chloro-7-iodoquinoline-3-carboxylate

In this work, we report the synthesis of a novel quinoline derivative, ethyl 4-chloro-7-iodoquinoline-3-carboxylate (CIQC), and its structural, conformational and vibrational characterization. The compound was studied in its neat solid phases (crystalline and low-temperature amorphous phases) and as an isolated species in a cryogenic argon matrix (at ∼15 K). Infrared spectroscopy and single crystal X-ray diffraction were the chosen experimental techniques. The conformational space and the vibrational spectra of the isolated molecules of the compound were also investigated theoretically at the B3LYP/LANL2DZ+cc-pVDZ level of approximation.The CIQC molecule exists in four different conformers, with predicted populations of 42:25:17:16% at room temperature (rt). The rt equilibrium conformational mixture was successfully trapped in an argon matrix, at 15 K, and the vibrational signatures of the conformers were determined. Upon annealing of the matrix of the compound at higher temperatures (∼40 K), conversion of the higher energy forms into the most stable conformer was found to take place, in consonance with the low predicted barriers for conformational isomerization. Sublimation of the host matrix argon atoms (at ∼43 K) led to production of a low-temperature amorphous state of CIQC, containing the lowest but also the higher energy conformers. At T ∼233–243 K, the amorphous rearranged to the crystalline state, whose molecular unit corresponds to the most stable CIQC conformer, as shown both by infrared spectroscopy and single crystal X-ray diffraction.At room temperature CIQC crystallizes in the hexagonal P63/m space group, with a=b=17.7928(2) Å, and c=6.9830(1) Å. The molecules lie on a crystallographic mirror plane and are stacked in layers along the c-axis. The main packing motif consists of a group of three molecules, related by a three-fold rotation, joined together by weak C–H ⋯ O hydrogen bonds.

Distinctive features arising in maximally random jammed packings of superballs

Dense random packings of hard particles are useful models of granular media and are closely related to the structure of nonequilibrium low-temperature amorphous phases of matter. Most work has been done for random jammed packings of spheres and it is only recently that corresponding packings of nonspherical particles (e.g., ellipsoids) have received attention. Here we report a study of the maximally random jammed (MRJ) packings of binary superdisks and monodispersed superballs whose shapes are defined by |x1|2p+...+|xd|2p<or=1 with d=2 and 3, respectively, where p is the deformation parameter with values in the interval (0,infinity). As p increases from zero, one can get a family of both concave (0<p<0.5) and convex (p>or=0.5) particles with square symmetry (d=2), or octahedral and cubic symmetry (d=3). In particular, for p=1 the particle is a perfect sphere (circular disk) and for p-->infinity the particle is a perfect cube (square). We find that the MRJ densities of such packings increase dramatically and nonanalytically as one moves away from the circular-disk and sphere point (p=1). Moreover, the disordered packings are hypostatic, i.e., the average number of contacting neighbors is less than twice the total number of degrees of freedom per particle, and yet the packings are mechanically stable. As a result, the local arrangements of particles are necessarily nontrivially correlated to achieve jamming. We term such correlated structures "nongeneric." The degree of "nongenericity" of the packings is quantitatively characterized by determining the fraction of local coordination structures in which the central particles have fewer contacting neighbors than average. We also show that such seemingly "special" packing configurations are counterintuitively not rare. As the anisotropy of the particles increases, the fraction of rattlers decreases while the minimal orientational order as measured by the tetratic and cubatic order parameters increases. These characteristics result from the unique manner in which superballs break their rotational symmetry, which also makes the superdisk and superball packings distinctly different from other known nonspherical hard-particle packings.

A Critical Size of Silicon Nano‐Anodes for Lithium Rechargeable Batteries

Due to the high theoretical capacity (ca. 4200 mAhg ) of Si when Li4.4Si is formed, it has been extensively investigated for use as a high-capacity anode material that can replace graphite, which is currently used (372 mAhg ). However, Si exhibits significant volume changes (> 360%) during Li alloying and dealloying. These changes cause cracking and crumbling of the electrode material and a consequent loss of electrical contact between individual particles and hence severe capacity drop. However, such mechanical strain induced by volume change can be reduced by employing smaller particles. To this end, synthetic methods such as spark ablation, aerogel techniques, and sputtering have been employed. Formation of crystalline Si nanoparticles requires higher temperatures due to the more covalent nature of these particles compared to Ge particles, and at low temperature amorphous phases become more common. The first commonly recognized successful production of Si nanoclusters was reported byHeath et al. They showed that Si nanocrystals capped with alkyl groups can be produced by reduction of SiCl4 and RSiCl3 (R=H, C8H17) according to the reaction SiCl4+RSiCl3+Na!Si+NaCl. This process was carried out at high temperature (385 8C) and high pressure (>100 atm) in a steel bomb fitted into a heating mantle. A process that utilizes SiCl4 reduction at room temperature under an inert atmosphere was initially reported by Kauzlarich et al. However, the drawback of their method was that the product obtained at room temperature was not fully crystallized and was severely capped with alkyl terminators. Moreover, an annealing process above 900 8C is required to obtain the crystalline phase. Similar solution syntheses have been reported at low or high temperature after reducing Si salts with LiAlH4 [13,14] or alkyl silanes. However, all of these methods produce a broad particle size distribution or involve aggregation of the nanoparticles. Furthermore, they all yield amounts of material too small for use in anode production for lithium secondary batteries. We now report a synthetic method using reverse micelles at high pressure and temperature in a bomb that produces Si nanoparticles (n-Si) with various particle sizes without aggregation and thus enables the optimal nanoparticle size for use in anode materials to be chosen. Figure 1 shows the XRD pattern and TEM images of n-Si prepared with trimethyloctadecylammonium bromide (OTAB) surfactant. The XRD pattern clearly shows forma-

Investigation of dynamic glass transitions and structural transformations in cryovacuum condensates of ethanol

An IR spectrometric investigation of the dynamic glass transition of ethanol from the rotationally disordered crystal to the orientationally disordered crystal is carried out. The samples considered are thin films formed from the gas phase at a substrate temperature of T=16K. The measurements are performed using the experimental apparatus which has been described in detail in our recent work. The sample thickness was d=2μm, and the typical rate of annealing is approximately 10K∕min. The results are compared with the phase diagram of solid ethanol proposed by M.A. Ramos et al. We observe good agreement between the temperature intervals of existence of the amorphous and crystalline states. The low-temperature amorphous phase (12–70K) is described by the present authors as amorphous solid ethanol by analogy with the amorphous solid water.

Conformational Flexibility, UV−Induced Decarbonylation, and FTIR Spectra of 1-Phenyl-1,2 Propanedione in Solid Xenon and in the Low Temperature Amorphous Phase

1-Phenyl-1,2-propanedione has been isolated in low-temperature xenon matrixes and studied by FTIR spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In good agreement with previous electron diffraction data [Shen, Q.; Hagen, K. J. Phys. Chem. 1993, 97, 985], the calculations predicted the existence of only one stable conformation for the compound, in which the O=C-C=O dihedral angle is 135.6 degrees. On the other hand, the experimental data clearly reveals that, in the as-deposited xenon matrixes (T = 20 K), there is a distribution of molecules with different O=C-C=O dihedral angles around the equilibrium value. This distribution results from the efficient trapping of the conformational distribution existing in the gas phase, prior to deposition, which is determined by the low frequency, large amplitude torsional vibration around the C-C central bond. Upon annealing to higher temperatures (T approximately 45 K), the initially trapped conformational distribution can be modified in a certain degree, favoring more polar structures (corresponding to smaller O=C-C=O dihedral angles), as a result of the interactions with the matrix media. Irradiation of the matrix with UV light (lambda > 235 nm) led to decarbonylation of the compound, with generation of acetophenone and carbon monoxide, with an almost complete consumption of the reagent after 1100 min of irradiation (k = 2.8 x 10(-2) min.(-1)). Aggregation of the compound resulting from the matrix warming was also investigated, providing useful information for interpretation of the spectroscopic data obtained for the low-temperature amorphous state of the neat compound.

Structure and bonding in single- and two-phase alumina-based glasses

Pulsed neutron and high energy X-ray diffraction experiments on single- and two-phase Al2O3–Y2O3 and single-phase Al2O3–La2O3 glasses suggest that a polyamorphic phase transition occurs via changes in the Y–O coordination and connectivity. The transformation from a high temperature to a low temperature amorphous phase is mainly associated with the formation of YO8 polyhedra at the expense of YO7 polyhedra. The transition produces a more ordered network structure with increased oxygen connectivity, while maintaining the overall metal∶oxygen stoichiometry. It is estimated that for the two-phase sample studied ∼12% of the Y ions had transformed to the higher coordinate form in the supercooled liquid as the onset of the glass transition was reached.

Thermodynamic behavior of a model covalent material described by the environment-dependent interatomic potential

Using molecular-dynamics simulations we study the thermodynamic behavior of a single-component covalent material described by the recently proposed environment-dependent interatomic potential (EDIP). The parametrization of EDIP for silicon exhibits a range of unusual properties typically found in more complex materials, such as the existence of two structurally distinct disordered phases, a density increase upon melting of the low-temperature amorphous phase, and negative thermal-expansion coefficients for both the crystal (at high temperatures) and the amorphous phase (at all temperatures). Structural differences between the two disordered phases also lead to a first-order transition between them, which suggests the existence of a second critical point, as is believed to exist for amorphous forms of frozen water. For EDIP-Si, however, the unusual behavior is associated not only with the open nature of tetrahedral bonding but also with a competition between fourfold (covalent) and fivefold (metallic) coordination. The unusual behavior of the model and its unique ability to simulate the liquid/amorphous transition on molecular-dynamics time scales make it a suitable prototype for fundamental studies of anomalous thermodynamics in disordered systems.

Spatial structure in low-temperature amorphous phases of water

The spatial (local) structure in liquid water at ambient conditions has been recently determined in computer simulation and neutron diffraction studies using the spatial distribution functions between atoms. The spatial distribution functions of oxygen atoms are analyzed for the low-temperature amorphous phases of water obtained in MD simulations with the TIP4P potential. These structural data reveal the important role played by the nontetrahedral, interstitial coordination of H 2O molecules in phase transitions of low-temperature water.

Infrared Intensity Measurements of Cryodeposited Thin Films of NH3, NH4HS, H2S, and Assignments of Absorption Bands

Interferometric infrared spectral transmission measurements from 60 to 10 000 cm−1 were made for thin films of NH3, NH4HS, and H2S cryodeposits, and recorded as a function of thickness and temperature from 88 K to evaporation points. Integrated band intensities were measured and are reported for all major absorptions. Assignments for lattice and internal fundamental modes are discussed. Particular attention is devoted to the various reported phases of solid NH3, and it is concluded that three phases are supported by experimental evidence: the stable cubic phase, a low temperature amorphous phase, and an intermediate temperature metastable phase. Results and changes of the spectra as a function of temperature will be summarized. Intercomparisons of the spectra obtained for the three cryodeposits are made.