Relating composition, structural order, entropy and transport in multi-component molten salts

Molecular dynamics simulations of the LiF-BeF(2) molten salt mixture are used to establish relationships between composition, structural order, entropy, and transport properties of multi-component ionic liquids. A sharp rise in tetrahedral order associated with formation of the fluoroberyllate network occurs for compositions with BeF(2) concentrations greater than that of the Li(2)BeF(4)-BeF(2) eutectic. The excess entropy of the liquid in this regime, within the pair correlation approximation, is strongly correlated with the local tetrahedral order. The different degree of participation of beryllium, fluorine, and lithium ions in the cooperative dynamics of the fluoroberyllate network can be related to the degree of deviation from Rosenfeld-type excess entropy scaling, with the lithium ions remaining essentially unaffected by the liquid state network. We demonstrate that the deviations from Nernst-Einstein and Stokes-Einstein behaviour emerge only in temperature-composition regimes where tetrahedral order strongly correlates with the pair entropy. Implications for understanding structure-property relationships in other ionic liquids, such as molten salts, oxide melts, and RTILs are considered.     

The vibration-rotation emission spectrum of hot BeF2

The high-resolution infrared emission spectrum of BeF2 vapor at 1000 degrees C was rotationally analyzed with the assistance of large-scale ab initio calculations using the coupled-cluster method including single and double excitations and perturbative inclusion of triple excitations, in conjunction with correlation-consistent basis sets up to quintuple-zeta quality. The nu3 fundamental band, the nu1+nu2, nu1+nu3, and 2nu2+nu3 combination bands, and 18 hot bands were assigned. The symmetric stretching (nu1), bending (nu2), and antisymmetric stretching (nu3) mode frequencies were determined to be 769.0943(2), 342.6145(3), and 1555.0480(1) cm-1, respectively, from the band origins of the nu3, nu1+nu3, and nu1+nu2 bands. The observed vibrational term values and B rotational constants were fitted simultaneously to an effective Hamiltonian model with Fermi resonance taken into account, and deperturbed equilibrium vibrational and rotational constants were obtained for BeF2. The equilibrium rotational constant (Be) was determined to be 0.235 354(41) cm-1, and the associated equilibrium bond distance (re) is 1.3730(1) A. The results of our ab initio calculations are in remarkably good agreement with those of our experiment, and the calculated value was 1.374 A for the equilibrium bond distance (re). As in the isoelectronic CO2 molecule, the Fermi resonance in BeF2 is very strong, and the interaction constant k122 was found to be 90.20(4) cm-1.     

A first-principles description of liquid BeF2 and its mixtures with LiF: 1. Potential development and pure BeF2

The construction of an interaction potential for BeF2 and its mixtures with LiF on a purely first-principles basis is described. The quality of the representation of the forces on the ions obtained from ab initio electronic structure calculations by various potentials, which include many-body interaction effects to different extents, are considered. The predictions of the properties of pure BeF2 obtained in simulations with a polarizable potential are then compared with experimental values. In the subsequent paper, a more extensive comparison of the predicted properties of LiF-BeF2 mixtures with experiment is considered.     

复合氟化物Li2BeF4的水热合成、晶化动力学研究及结构表征

通过中温水热法合成出复合氟化物Li₂BeF₄,并对合成中反应物的配比、反应温度和反应时间等条件进行了研究.XRD测试结果表明产物物相纯净,SEM显示产物为250μm的六方柱形晶体;IR和XPS测试表明产物中羟基和氧含量低.实验发现了晶化曲线的振荡现象,并做了初步的解释.     

Conductivity-viscosity-structure: unpicking the relationship in an ionic liquid

The relationships between the ionic mobility, the viscosity, and the atomic-scale structure are investigated in computer simulations of mixtures of LiF and the network glass-forming material BeF(2). The simulations span a wide range of compositions, across which the fluidity of the system changes greatly due to the break-up of the Be-F network by the addition of the LiF. The relationship between the conductivity and viscosity passes from that expected for independently diffusing ions in the dilute mixtures to strongly decoupled Li+ migration through a viscous network at higher concentrations. The transition between these régimes is linked to the changing local and intermediate-scale structure in the melts. The decoupling phenomenon is associated with the appearance of migration channels in the network which leads to cooperative effects in the Li+ migration.     

某些离解能、电子亲合能等的G2计算与评价

PoPle及其合作者创立的Gaussian再简称GZ）理论［‘－’］，以其相对可靠的化学精度和相应较小的计算量已经引起了实验和理论化学家们的广泛关注问．p。ple等人在他们的GZ文章中强调了GZ的理论计算结果在研究离解能等化学问题中与精确实验数据之间的偏差普遍不大于全8．狄J规厂‘．我们近期的研究表明＊’1，＊2和优（＊则在计算一般化学反应能量中，绝大多数情况下，分别都能保证结果与实验偏差在全8．4和士13kJ·mol‘以内．近年来，已有大量的研究工作表明，GZ的理论结果已广泛用于未知实验数据的预测、已有实验数据的评价和修正等…     

Reactions of beryllium halides in liquid ammonia: the tetraammineberyllium cation [Be(NH3)4]2+, its hydrolysis products, and the action of Be2+ as a fluoride-ion acceptor

The first structural characterization of the text-book tetraammineberyllium(II) cation [Be(NH(3))(4)](2+), obtained in the compounds [Be(NH(3))(4)](2)Cl(4)?17NH(3) and [Be(NH(3))(4)]Cl(2), is reported. Through NMR spectroscopic and quantum chemical studies, its hydrolysis products in liquid ammonia were identified. These are the dinuclear [Be(2)(μ-OH)(NH(3))(6)](3+) and the cyclic [Be(2)(μ-OH)(2)(NH(3))(4)](2+) and [Be(3)(μ-OH)(3)(NH(3))(6)](3+) cations. The latter species was isolated as the compound [Be(3)(μ-OH)(3)(NH(3))(6)]Cl(3)?7NH(3). NMR analysis of solutions of BeF(2) in liquid ammonia showed that the [BeF(2)(NH(3))(2)] molecule was the only dissolved species. It acts as a strong fluoride-ion acceptor and forms the [BeF(3)(NH(3))](-) anion in the compound [N(2)H(7)][BeF(3)(NH(3))]. The compounds presented herein were characterized by single-crystal X-ray structure analysis, (9)Be, (17)O, and (19)F?NMR, IR, and Raman spectroscopy, deuteration studies, and quantum chemical calculations. The extension of beryllium chemistry to the ammine system shows similarities but also decisive differences to the aquo system.     

Isomorphism of anhydrous tetrahedral halides and silicon chalcogenides: energy landscape of crystalline BeF2, BeCl2, SiO2, and SiS2

We employ periodic density functional theory calculations to compare the structural chemistry of silicon chalcogenides (silica, silicon sulfide) and anhydrous tetrahedral halides (beryllium fluoride, beryllium chloride). Despite the different formal oxidation states of the elements involved, the divalent halides are known experimentally to form crystal structures similar to known SiX2 frameworks; the rich polymorphic chemistry of SiO2 is however not matched by divalent halides, for which a very limited number of polymorphs are currently known. The calculated energy landscapes yield a quantitative match between the relative polymorphic stability in the SiO2/BeF2 pair, and a semiquantitative match for the SiS2/BeCl2 pair. The experimentally observed polymorphs are found to lie lowest in energy for each composition studied. For the two BeX2 compounds studied, polymorphs not yet synthesized are predicted to lie very low in energy, either slightly above or even in between the energy of the experimentally observed polymorphs. The experimental lack of polymorphism for tetrahedral halide materials thus does not appear to stem from a lack of low-energy polymorphs but more likely is the result of a lack of experimental exploration. Our calculations further indicate that the rich polymorphic chemistry of SiO2 can be potentially matched, if not extended, by BeF2, provided that milder synthetic conditions similar to those employed in zeolite synthesis are developed for BeF2. Finally, our work demonstrates that both classes of materials show the same behavior upon replacement of the 2p anion with the heavier 3p anion from the same group; the thermodynamic preference shifts from structures with large rings to structures with larger fractions of small two and three membered rings.     

Excess entropy scaling of transport properties in network-forming ionic melts (SiO(2) and BeF(2))

The regime of validity of Rosenfeld excess entropy scaling of diffusivity and viscosity is examined for two tetrahedral, network-forming ionic melts (BeF(2) and SiO(2)) using molecular dynamics simulations. With decrease in temperature, onset of local caging behavior in the diffusional dynamics is shown to be accompanied by a significant increase in the effect of three-body and higher-order particle correlations on the excess entropy, diffusivity, ionic conductivity, and entropy-transport relationships. The signature of caging effects on the Rosenfeld entropy scaling of transport properties is a distinctly steeper dependence of the logarithm of the diffusivity on the excess entropy in ionic melts. This is shown to be true also for a binary Lennard-Jones glassformer, based on available results in the literature. Our results suggest that the onset of a landscape-influenced regime in the dynamics is correlated with this characteristic departure from Rosenfeld scaling. The breakdown of the Nernst-Einstein relation in the ionic melts can also be correlated with the emerging cooperative dynamics.     

Cation-anion-water interactions in aqueous mixtures of imidazolium based ionic liquids

We have examined the cation-anion-water interactions in aqueous mixtures of imidazolium ionic liquids (ILs) over the whole composition range using FTIR spectroscopy. Changes in the peak positions or band areas of OH vibrational modes of water and CH vibrational modes of imidazolium cation as a function of IL concentration indicated a diminishing trend in hydrogen-bonding network of water and qualitative changes in solution structures. ¹H NMR chemical shifts of C(2)H, HC(4)C(5)H and alkyl chain protons of imidazolium cation provided useful information about the comparative strength of cation-anion-water interactions.     

Proton conductivity in TaH(PO4)2 · 2H2O + SiO2 composite electrolytes

The composite electrolytes of composition (1 ? x)TaH(PO₄)₂ · 2H₂O/xSiO₂ (x = 0.2–0.4) are synthesized, and their transport properties are characterized over a wide temperature range. Doping with highly dispersed silica only insignificantly changes the proton conductivity of tantalum hydrogenphosphate below 370 K; above 820 K, the conductivity increases. The evolution of the phase composition of TaH(PO₄)₂ · 2H₂O and its base materials during thermolysis is studied.     

Waterlike structural and excess entropy anomalies in liquid beryllium fluoride

The relationship between structural order metrics and the excess entropy is studied using the transferable rigid ion model (TRIM) of beryllium fluoride melt, which is known to display waterlike thermodynamic anomalies. The order map for liquid BeF2, plotted between translational and tetrahedral order metrics, shows a structurally anomalous regime, similar to that seen in water and silica melt, corresponding to a band of state points for which average tetrahedral (q(tet)) and translational (tau) order are strongly correlated. The tetrahedral order parameter distributions further substantiate the analogous structural properties of BeF2, SiO2, and H2O. A region of excess entropy anomaly can be defined within which the pair correlation contribution to the excess entropy (S2) shows an anomalous rise with isothermal compression. Within this region of anomalous entropy behavior, q(tet) and S2 display a strong negative correlation, indicating the connection between the thermodynamic and the structural anomalies. The existence of this region of excess entropy anomaly must play an important role in determining the existence of diffusional and mobility anomalies, given the excess entropy scaling of transport properties observed in many liquids.     

Compounds of superatom clusters: preferred structures and significant nonlinear optical properties of the BLi6-X (X = F, LiF2, BeF3, BF4) motifs

A new type of superalkali-(super)halogen compound, BLi6-X (X = F, LiF2, BeF3, BF4), is theoretically predicted. The interaction between superalkali BLi6 and different shaped superhalogen X is found to be strong and ionic in nature. Bond energies of these BLi6-X species are in the range of 151.3-220.6 kcal/mol at the CCSD(T)/aug-cc-pVDZ level, which are much larger than the traditional ionic bond energy of 130.1 kcal/mol for LiF. Furthermore, because of their delocalized electron character, these superalkali-(super)halogen species exhibit extraordinarily large first hyperpolarizabilities with beta0 ranging from 5166.5 to 17791.0 au. Besides, the examination of the variation of nonlinear optical (NLO) properties with the size of (BLi6-BeF3)n assemblies shows the dependence of NLO properties on the chain length of (BLi6-BeF3)n. The present investigation gives hints to scientists in extending the research in atomic dimension to direct the interaction between superatoms, and using superatoms as building blocks to synthesize novel meaningful materials with unusual properties such as nonlinear optical properties.     

Structural characterization of glassy phases in the system Na2O-Ga2O3-P2O5 by MAS and solution NMR and vibrational spectroscopy: II. Structure of the phosphate network

The structure of the phosphate network of glasses in the system Na2O-Ga2O3-P2O5 has been investigated as a function of the Na/Ga molar ratio and the phosphate composition corresponding to a mono, di, tri, tetra and meta phosphate stoichiometry. The glass is made of phosphate molecular groups of different lengths linked by the cations with rather ionic (Na) or more covalent (Ga) bonds except in the case of the orthophosphate composition for which we only found isolated PO4(3-) ions. The vibrational spectra are sensitive to composition variations but the band width and the couplings between the different groups prevent any quantitative determination. 31P MAS-NMR gives an in-situ information on the P environment in the glass but the signals are often large and ill defined so that the assignment is not at all straightforward. On the other hand, 31P solution NMR gives sharper signals, allowing more quantitative determinations but the dissolution process always introduces some indeterminacy on the real glass structure which can be minimized by a careful preparation of the solution.     

Spectroscopic study of (two-dimensional) molecule-based magnets: [M(II)(TCNE)(NCMe)2][SbF6] (M = Fe, Mn, Ni)

The M-[TCNE] (M = 3d metal; TCNE = tetracyanoethylene) system is one of the most interesting classes of molecule-based magnets, exhibiting a plethora of compositions and structures (inorganic polymer chains, 2D layers, 3D networks, and amorphous solids) with a wide range of magnetic ordering temperatures (up to 400 K). A systematic study of vibrational (both infrared and, for the first time, Raman) properties of the family of new TCNE-based magnets of M(II)(TCNE) (NCMe)(2)[SbF(6)] [M = Mn, Fe, Ni] composition is discussed in conjunction with their magnetic behavior and newly reso-lved crystal structures. The vibrational properties of the isolated TCNE(●-) anion in the paramagnetic Bu(4)N [TCNE(●-)] salt and recently characterized 2D layered magnet Fe(II)(TCNE)(NCMe)(2)[FeCl(4)] are also reported for comparison. Additionally, a linear correlation between ν(C=C) (a(g)) frequency of the TCNE ligand and its formal charge Z (the spin density on the π* orbital), Z = [1571 - ν(C=C) (a(g))]/154.5 [e], is presented. It is shown that monitoring Z by Raman spectroscopy is of great use in providing information that allows understanding the peculiarity of the superexchange interaction in M-[TCNE] magnets and establishing the structure-magnetic properties correlations in this class of magnetic material.     

Chemical bonding in TiSb(2) and VSb(2): a quantum chemical and experimental study

The chemical bonding in the isostructural intermetallic compounds TiSb2 and VSb2, crystallizing in the CuAl2 type, was investigated by means of quantum chemical calculations, particularly the electron localization function (ELF), as well as by Raman spectroscopy, Hall effect and conductivity measurements on oriented single crystals, and high-pressure X-ray powder diffraction. The homogeneity ranges of the compounds were determined by powder X-ray diffraction, WDXS, and DSC measurements. TiSb2 exhibits no significant homogeneity range, while VSb2 shows a small homogeneity range of approximately 0.3 at. %. According to the ELF calculations, the Sb atoms form dumbbells via a two-center two-electron bond, while the T atoms (T = Ti, V) build up chains along the crystallographic c-axis. Both building units are connected by covalent T-Sb-T three-center bonds, thus forming a three-dimensional network. The strength of the bonds involving Sb was determined by fitting a force constant model to the vibrational mode frequencies observed by polarized Raman measurements on oriented single crystals. The resulting bond order of the Sb2 dumbbells is 1, while the strength of the three-center bonds resembles a bond order of 1.5. The weak pressure dependence of the c/a ratio confirms the slightly different bonding picture in TiSb2 compared to that in CuAl2. Electrical transport measurements show the presence of free charge carriers, as well as a metal-like temperature dependence of the electrical resistivity.     

Mode-specific photoelectron scattering effects on CO2(+)(C2Sigmag+) vibrations

Using high-resolution photoelectron spectroscopy, we have determined the energy dependent vibrational branching ratios for the symmetric stretch [v+ = (100)], bend [v+ = (010)], and antisymmetric stretch [v+ = (001)], as well as several overtones and combination bands in the 4sigmag(-1) photoionization of CO2. Data were acquired over the range from 20-110 eV, and this wide spectral coverage highlighted that alternative vibrational modes exhibit contrasting behavior, even over a range usually considered to be dominated by atomic effects. Alternative vibrational modes exhibit qualitatively distinct energy dependences, and this contrasting mode-specific behavior underscores the point that vibrationally resolved measurements reflect the sensitivity of the electron scattering dynamics to well-defined changes in molecular geometry. In particular, such energy-dependent studies help to elucidate the mechanism(s) responsible for populating the symmetry forbidden vibrational levels [i.e., v+ =( 010), (001), (030), and (110)]. This is the first study in which vibrationally resolved data have been acquired as a function of energy for all of the vibrational modes of a polyatomic system. Theoretical Schwinger variational calculations are used to interpret the experimental data, and they indicate that a 4sigmag-->ksigmau shape resonance is responsible for most of the excursions observed for the vibrational branching ratios. Generally, the energy dependent trends are reproduced well by theory, but a notable exception is the symmetric stretch vibrational branching ratio. The calculated results display a strong peak in the vibrational branching ratio while the experimental data show a pronounced minimum. This suggests an interference mechanism that is not accounted for in the single-channel adiabatic-nuclei calculations. Electronic branching ratios were also measured and compared to the vibrational branching ratios to assess the relative contributions of interchannel (i.e., Herzberg-Teller) versus intrachannel (i.e., photoelectron-mediated) coupling.     

Theoretical Study on the Potential Energy Curve and Vibration-rotation Spectra of BeF Radical

The potential energy curve (PEC) of BeF(X2Σ+) radical is investigated by using the complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach over the internuclear separation range from 0.0522 to 2.0472 nm. The PEC is fitted to the analytic Murrell-Sorbie function, which is employed to accurately determine the spectroscopic parameters. The present D0, De, Re, ωe, ωeχe, αe and Be are 6.14 eV, 6.22 eV, 0.1372 nm, 1236.12 cm-1, 9.11 cm-1, 0.0175 cm-1 and 1.4651 cm-1, respectively. These parameters have been compared with those of previous investigations reported in the literature. With PEC determined at the present level of theory, a total of 75 vibrational states have been predicted for the first time by numerically solving the radial Schrdinger equation of nuclear motion using the Numerov method. For each vibrational state, the complete vibrational levels, classical turning points, inertial rotation and centrifugal distortion constants are determined for the first time. Comparing with the available experiments and other theories, we find that the present spectroscopic parameter and molecular constant results are more accurate and complete than the previous theoretical investigations.     

Superstructure in the Metastable Intermediate‐Phase Li2/3FePO4 Accelerating the Lithium Battery Cathode Reaction

LiFePO₄ is an important cathode material for lithium‐ion batteries. Regardless of the biphasic reaction between the insulating end members, Li_xFePO₄, x≈0 and x≈1, optimization of the nanostructured architecture has substantially improved the power density of positive LiFePO₄ electrode. The charge transport that occurs in the interphase region across the biphasic boundary is the primary stage of solid‐state electrochemical reactions in which the Li concentrations and the valence state of Fe deviate significantly from the equilibrium end members. Complex interactions among Li ions and charges at the Fe sites have made understanding stability and transport properties of the intermediate domains difficult. Long‐range ordering at metastable intermediate eutectic composition of Li_2/3FePO₄ has now been discovered and its superstructure determined, which reflected predominant polaron crystallization at the Fe sites followed by Li⁺ redistribution to optimize the Li? Fe interactions.