Abstract:The cavity inside fullerenes provides a unique environment for the study of isolated atoms and molecules. We report encapsulation of hydrogen fluoride inside C 60 using molecular surgery to give the endohedral fullerene HF@C 60 . The key synthetic step is the closure of the open fullerene cage while minimizing escape of HF. The encapsulated HF molecule moves freely inside the cage and exhibits quantization of its translational and rotational degrees of freedom, as revealed by inelastic neutron scattering and infrared spectroscopy. The rotational and vibrational constants of the encapsulated HF molecules were found to be redshifted relative to free HF. The NMR spectra display a large 1 H-19 F Jcoupling typical of an isolated species. The dipole moment of HF@C 60 was estimated from the temperature-dependence of the dielectric constant at cryogenic temperatures and showed that the cage shields around 75% of the HF dipole.Molecular endofullerenes consist of fullerene cages encapsulating small molecules, which are free to rotate and translate inside the cage. 1 The dihydrogen and water endofullerenes H 2 @C 60 , H 2 O@C 60 , and their isotopologues, have been synthesized by the procedure known as 'molecular surgery', in which synthetic operations are used to open a hole in the fullerene allowing encapsulation of the guest, followed by a suturing technique to reform the pristine fullerene shell. [2][3][4] Recently the approach has been extended to C 70 and C 59 N. [5][6][7] The confined molecules display quantization of their coupled translational and rotational degrees of freedom, and exhibit phenomena such as nuclear spin isomerism and orthopara conversion. [8][9][10][11][12] Recently it was shown that nuclear spin conversion of the encapsulated water molecules in H 2 O@C 60 leads to a change in the dielectric constant of the material. 13 One system of great interest is HF@C 60 , in which each fullerene cage contains a single hydrogen fluoride (HF) molecule. This material offers the possibility to study the spectroscopic properties of nearisolated and freely rotating HF molecules under a wide range of conditions, free from the complications of dimerization and hydrogen bonding. Predictions of the properties of HF@C 60 have been made using classical, 14 semiempirical 15,16 and quantum chemistry techniques. [17][18][19][20] Furthermore it has been postulated that endofullerenes containing freely rotating electric dipoles could exhibit ferroelectricity, due to cooperative alignment of the interacting electric dipole moments. 21 2The first examples of open-cage endofullerenes encapsulating a hydrogen fluoride molecule have recently appeared, including HF@1. 22,23 Herein we report the successful suturing of HF@1 to give the closed-cage species HF@C 60 . We present NMR, infrared, and neutron scattering data on HF@C 60 which show that the translational and rotational motions of the HF molecule inside the cage are quantized. Interactions with the cage modify the rotational and vibrational constants of the encapsula...

The material class of skutterudites is believed to have strong potential for thermoelectric application due to the very low thermal conductivity of the filled structures. It is generally assumed that the atoms filling the skutterudite cages act as 'rattlers' and essentially induce a disordered lattice dynamics referred to as 'phonon glass'. Here, we present neutron spectroscopy experiments and ab initio computational work on phonons in LaFe(4)Sb(12) and CeFe(4)Sb(12). Our results give unequivocal evidence of essentially temperature-independent lattice dynamics with well-defined phase relations between guest and host dynamics, indicative of a quasi-harmonic coupling between the guests and the host lattice. These conclusions are in disagreement with the 'phonon glass' paradigm based on individual 'rattling' of the guest atoms. These findings should have an essential impact on the design and improvement of thermoelectric materials and on the development of microscopic models needed for these efforts.

SrFeO(2.5) and SrCoO(2.5) are able to intercalate oxygen in a reversible topotactic redox reaction already at room temperature to form the cubic perovskites Sr(Fe,Co)O(3), while CaFeO(2.5) can only be oxidized under extreme conditions. To explain this significant difference in low temperature oxygen mobility, we investigated the homologous SrFeO(2.5) and CaFeO(2.5) by temperature dependent oxygen isotope exchange as well as by inelastic neutron scattering (INS) studies, combined with ab initio (DFT) molecular dynamical calculations. From (18)O/(16)O isotope exchange experiments we proved free oxygen mobility to be realized in SrFeO(x) already below 600 K. We have also evidence that low temperature oxygen mobility relies on the existence of specific, low energy lattice modes, which trigger and amplify oxygen mobility in solids. We interpret the INS data together with the DFT-based molecular dynamical simulation results on SrFeO(2.5) and CaFeO(2.5) in terms of an enhanced, phonon-assisted, low temperature oxygen diffusion for SrFeO(3-x) as a result of the strongly reduced Fe-O-Fe bond strength of the apical oxygen atoms in the FeO(6) octahedra along the stacking axis. This dynamically triggered phenomenon leads to an easy migration of the oxide ions into the open vacancy channels and vice versa. The decisive impact of lattice dynamics, giving rise to structural instabilities in oxygen deficient perovskites, especially with brownmillerite-type structure, is demonstrated, opening new concepts for the design and tailoring of low temperature oxygen ion conductors.

The antiferromagnetic structures of the layered oxychalcogenides (Sr(1-x)Ba(x))(2)CoO(2)Cu(2)S(2) (0 ≤ x ≤ 1) have been determined by powder neutron diffraction. In these compounds Co(2+) is coordinated by four oxide ions in a square plane and two sulfide ions at the apexes of an extremely tetragonally elongated octahedron; the polyhedra share oxide vertexes. The magnetic reflections present in the diffraction patterns can in all cases be indexed using a √2a × √2a × c expansion of the nuclear cell, and nearest-neighbor Co(2+) moments couple antiferromagnetically within the CoO(2) planes. The ordered magnetic moment of Co(2+) in Sr(2)CoO(2)Cu(2)S(2) (x = 0) is 3.8(1) μ(B) at 5 K, consistent with high-spin Co(2+) ions carrying three unpaired electrons and with an additional significant unquenched orbital component. Exposure of this compound to moist air is shown to result in copper deficiency and a decrease in the size of the ordered moment to about 2.5 μ(B); there is a strong correlation between the size of the long-range ordered moment and the occupancy of the Cu site. Both the tetragonal elongation of the CoO(4)S(2) polyhedron and the ordered moment in (Sr(1-x)Ba(x))(2)CoO(2)Cu(2)S(2) increase with increasing Ba content, and in Ba(2)CoO(2)Cu(2)S(2), which has Co(2+) in an environment that is close to purely square planar, the ordered moment of 4.5(1) μ(B) at 5 K is over 0.7 μ(B) larger than that in Sr(2)CoO(2)Cu(2)S(2), so the unquenched orbital component in this case is even larger than that observed in octahedral Co(2+) systems such as CoO. The experimental observations of antiferromagnetic ground states and the changes in properties resulting from replacement of Sr by Ba are supported by ab initio calculations on Sr(2)CoO(2)Cu(2)S(2) and Ba(2)CoO(2)Cu(2)S(2). The large orbital moments in these systems apparently result from spin-orbit mixing of the unequally populated d(xz), d(yz), and d(z(2)) orbitals, which are reckoned to be almost degenerate when the CoO(4)S(2) polyhedron reaches its maximum elongation. The magnitudes of the ordered moments in high-spin Co(2+) oxide, oxychalcogenide, and oxyhalide systems are shown to correlate well with the tetragonal elongation of the coordination environment. The large orbital moments lead to an apparently magnetostrictive distortion of the crystal structures below the Neél temperature, with the symmetry lowered from tetragonal I4/mmm to orthorhombic Immm and the size of the distortion correlating well with the size of the long-range ordered moment for all compositions and for temperature-dependent data gathered on Ba(2)CoO(2)Cu(2)S(2).

We present the results of a high-resolution neutron diffraction experiment with a fully deuterated methane hydrate type I at temperatures of 2, 100, and 150 K. Precise crystallographic parameters of the ice-like D2O lattice and the thermal parameters of the encaged methane molecules have been obtained. The parameters of the host lattice differ only slightly from values found for hydrates with asymmetric guests included, which leads to the conclusion that the host lattice of structure I is only a little adaptive. At low temperatures (2 K) the methane molecules in both types of cages present in structure I occupy positions in the center of the cages. At higher temperatures the thermal parameters in both types of cages reflect the surrounding cage geometries or more precisely the translational potentials of the cages. The orientational scattering length density of the CD4 molecules has been analyzed in terms of a multipole expansion with symmetry adapted functions [Press and Hüller, Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr. A29, 252 (1972); Press, ibid. A29, 257 (1972)]. In both types of cages we found only small modulations of a spherically symmetric scattering density accounting for almost free rotations of the methane molecules. The large and asymmetric cage leads to a somewhat more pronounced modulation of the orientational density than in the small dodecahedral cage. The orientational probability distribution function (PDF) remains nearly unchanged from 2 to 150 K. At 200 K we observed the time-resolved decomposition of the hydrate structure I into hexagonal ice Ih.

No abstract

Oxide ion conductors are technologically important materials because of their potential applications in oxygen sensors and pumps, as dense membranes for oxygen permeation, catalysts, and as electrolytes for solid oxide fuel cells (SOFCs). [1][2][3][4] To be efficient in various applications, candidate materials should possess a conductivity of at least 10 À2 S cm À1 at deviceoperating temperatures; currently commercially used yttriastabilized zirconia (YSZ) reaches this target at 700 8C.[1]Given the drive towards lowering device-operating temperatures, there is a strong impetus and a great challenge for materials chemists to develop materials with enhanced ionic mobility and superior low-temperature oxide ion conductivity. [5,6] A better understanding of generic structural features and pathways which facilitate ionic mobility at lower temperature is a key step in reaching this goal.Here we report a remarkably high oxide ion conductivity at low temperatures (300-500 8C) in an ordered pseudo-cubic 3 3 3 [8,9] By contrast and unusually, our materials crystallize as stable ordered superstructures, and do not undergo phase transitions to lower symmetry and lower conductivity polymorphs. Our ab initio molecular dynamics (AIMD) simulations reveal the structural features and mechanisms which facilitate the high oxide ion mobility at low temperatures, and provide conceptual insight readily applicable to other materials and structure types.The high-temperature cubic fluorite-type bismuth oxide, d-Bi 2 O 3 , with intrinsic oxygen vacancies, shows the highest oxide ion conductivity measured in any material (around 1 Scm À1 at 750 8C); [10] however, it is only thermodynamically stable in the narrow range between 730 and 824 8C.[11] There has been considerable interest in stabilizing the highly conducting d-Bi 2 O 3 phase by isovalent or aliovalent cation substitution to preserve oxide ion conductivity at lower temperatures. For example, 20 % substitution of Er into Bi 2 O 3 results in oxide ion conductivity of 2 10 À2 S cm À1 at 500 8C and 0.4 S cm À1 at 700 8C.[12] Double cation substitution has yielded even higher conductivities at low temperatures (300-500 8C); the best examples include Dy-W, [13] Pr-V, [7] and the recently reported La-Re [8] À3 -10 À2 S cm À1 at 300-400 8C, approaching the Cu-doped layered Bi 2 VO 5.5 (BICUVOX), which itself has the disadvantage of two-dimensional, anisotropic conductivity. Although the relative chemical instability of Bi oxides under reducing conditions has so far hampered their applications in SOFCs, the use of bilayer electrolytes can overcome this issue. [14] In addition to high oxide ion conductivity, bismuthbased oxides show electrocatalytic activity and therefore also have great potential for applications in electrochemical oxygen separation. [15,16] A common structural feature in the best d-Bi 2 O 3 -based oxide ion conductors reported so far is that doping stabilizes simple cubic structures with a % 5.5 and space group Fm " 3m. [7][8]13] By comparison, doped d-Bi 2 O 3 material...

Engineering lattice thermal conductivity requires to control the heat carried by atomic vibration waves, the phonons. The key parameter for quantifying it is the phonon lifetime, limiting the travelling distance, whose determination is however at the limits of instrumental capabilities. Here, we show the achievement of a direct quantitative measurement of phonon lifetimes in a single crystal of the clathrate Ba7.81Ge40.67Au5.33, renowned for its puzzling ‘glass-like’ thermal conductivity. Surprisingly, thermal transport is dominated by acoustic phonons with long lifetimes, travelling over distances of 10 to 100 nm as their wave-vector goes from 0.3 to 0.1 Å−1. Considering only low-energy acoustic phonons, and their observed lifetime, leads to a calculated thermal conductivity very close to the experimental one. Our results challenge the current picture of thermal transport in clathrates, underlining the inability of state-of-the-art simulations to reproduce the experimental data, thus representing a crucial experimental input for theoretical developments.