Rotational and Vibrational Dynamics of Interstitial Molecular Hydrogen

The calculation of the hindered roton-phonon energy levels of a hydrogen molecule in a confining potential with different symmetries is systematized for the case when the rotational angular momentum $J$ is a good quantum number. One goal of this program is to interpret the energy-resolved neutron time of flight spectrum previously obtained for H$_{2}$C$_{60}$. This spectrum gives direct information on the energy level spectrum of H$_2$ molecules confined to the octahedral interstitial sites of solid C$_{60}$. We treat this problem of coupled translational and orientational degrees of freedom a) by construction of an effective Hamiltonian to describe the splitting of the manifold of states characterized by a given value of $J$ and having a fixed total number of phonon excitations, b) by numerical solutions of the coupled translation-rotation problem on a discrete mesh of points in position space, and c) by a group theoretical symmetry analysis. Results obtained from these three different approaches are mutually consistent. The results of our calculations explain several hitherto uninterpreted aspects of the experimental observations, but show that a truly satisfactory orientational potential for the interaction of an H$_2$ molecule with a surrounding array of C atoms has not yet been developed.Comment: 53 pages, 9 figures, to appear in Phys. Rev B (in press). Phys. Rev. B (in press

Increasing 3D Supramolecular Order by Decreasing Molecular Order. A Comparative Study of Helical Assemblies of Dendronized Nonchlorinated and Tetrachlorinated Perylene Bisimides

A nonplanar, twisted, and flexible tetrachlorinated perylene bisimide (Cl4PBI) was functionalized with two AB3 minidendrons containing hydrogenated or semifluorinated dodecyl groups. The hydrogenated dendron was attached to the imide groups of Cl4PBI via m = 0, 1, and 2 methylenic units, whereas the dendron containing semifluorinated groups was attached via m = 3 or a di(ethylene oxide) linker (m = 2EO). The supramolecular structures of these compounds, determined by a combination of differential scanning calorimetry, X-ray diffraction, and solid-state NMR, were compared with those of nonchlorinated planar and rigid PBI reported previously, which demonstrated the thermodynamically controlled formation of 2D periodic arrays at high temperatures and 3D arrays at low temperatures. The molecularly less ordered Cl4PBI containing hydrogenated dendrons self-organize into exclusively 3D crystalline periodic arrays under thermodynamic control for m = 0 and 2, while the more highly molecularly ordered PBI produced less stable and ordered 3D crystals and also 2D assemblies. This induction of a higher degree of 3D order in supramolecular assemblies of the less well-ordered molecular building blocks was unanticipated. The semifluorinated dendronized Cl4PBI with m = 3 formed a 2D columnar hexagonal array under kinetic control, whereas the compound with m = 2EO formed an unusual 2D honeycomb-like hexagonal phase under thermodynamic control. These Cl4PBI compounds provide a new route to stable crystalline assemblies via thermodynamic control at lower temperatures than previously obtained with PBI, thus generating 3D order in an accessible range of temperature of interest for structural analysis and for technological applications

Vibrational Study of 13C-enriched C60 Crystals

The infrared (IR) spectrum of solid C60 exhibits many weak vibrational modes. Symmetry breaking due to 13C isotopes provides a possible route for optically activating IR-silent vibrational modes. Experimental spectra and a semi-empirical theory on natural abundance and 13C-enriched single crystals of C60 are presented. By comparing the experimental results with the theoretical results, we exclude this isotopic activation mechanism from the explanation for weakly active fundamentals in the spectra.Comment: Accepted for Phys. Rev. B, typeset in REVTEX v3.0 in LaTeX. Postscript file including figures is available at http://insti.physics.sunysb.edu/~mmartin/papers/c13twocol2.ps File with figures will be e-mailed by reques

Reversible Pressure-Induced Amorphization in Solid C70 : Raman and Photoluminescence Study

We have studied single crystals of $C_{70}$ by Raman scattering and photoluminescence in the pressure range from 0 to 31.1 GPa. The Raman spectrum at 31.1 GPa shows only a broad band similar to that of the amorphous carbon without any trace of the Raman lines of $C_{70}$. After releasing the pressure from 31.1 GPa, the Raman and the photoluminescence spectra of the recovered sample are that of the starting $C_{70}$ crystal. These results indicate that the $C_{70}$ molecules are stable upto 31.1 GPa and the amorphous carbon high pressure phase is reversible, in sharp contrast to the results on solid $C_{60}$. A qualitative explaination is suggested in terms of inter- versus intra-molecular interactions.Comment: To appear in Phys. Rev. Lett., 12 pages, RevTeX (preprint format), 3 figures available upon reques

Observation and Assignment of Silent and Higher Order Vibrations in the Infrared Transmission of C60 Crystals

We report the measurement of infrared transmission of large C60 single crystals. The spectra exhibit a very rich structure with over 180 vibrational absorptions visible in the 100 - 4000 cm-1 range. Many silent modes are observed to have become weakly IR-active. We also observe a large number of higher order combination modes. The temperature (77K - 300K) and pressure (0 - 25KBar) dependencies of these modes were measured and are presented. Careful analysis of the IR spectra in conjunction with Raman scattering data showing second order modes and neutron scattering data, allow the selection of the 46 vibrational modes C60. We are able to fit *all* of the first and second order data seen in the present IR spectra and the previously published Raman data (~300 lines total), using these 46 modes and their group theory allowed second order combinations.Comment: REVTEX v3.0 in LaTeX. 12 pages. 8 Figures by request. c60lon

Intra- site 4f-5d electronic correlations in the quadrupolar model of the gamma-alpha phase transition in Ce

As a possible mechanism of the $\gamma-\alpha$ phase transition in pristine cerium a change of the electronic density from a disordered state with symmetry Fm-3m to an ordered state Pa-3 has been proposed. Here we include on-site and inter- site electron correlations involving one localized 4f-electron and one conduction 5d-electron per atom. The model is used to calculate the crystal field of $\gamma$-Ce and the temperature evolution of the mean-field of $\alpha$-Ce. The formalism can be applied to crystals where quadrupolar ordering involves several electrons on the same site.Comment: 12 pages, 2 figures, 4 tables, submitted to Phys. Rev.

ICOSAHEDRAL ALLOYS : PHASE PURITY AND PHASON STRAINS

La diffraction des électrons et des rayons X ont été employé pour étudier des alloyages de Al avec les métaux transition. Nous trouvons la phase icosaèdre dans les alloyages de Al avec Mn, Cr, V, Mo, Ru, W, et Re. Nous montrons l'influence de Si et Ru dans les alloyages bimétallique. Nous discutons les avantages et les désavantages de différents schémas pour calculer les cliches de diffraction. Les distorsions dans les cliches de diffraction peut être expliqué par une nouvelle classe de défaut qui ne se trouve que dans les quasi-cristaux.We present a survey of x-ray and electron diffraction studies of Aluminum- Transition Meta1 alloys. The icosahedral phase is found in Al alloyed with Mn, Cr, V, Mo, Ru, W, and Re. The effect of adding small amounts of Si and Ru to the binary alloys is discussed. We review the advantages and disadvantages of various indexing schemes. Distortions of electron diffraction pictures are described in terms of phason strains in a quasilattice

High resolution X-ray scattering study of the multiply reentrant polar mesogen DB9ONO2

Liquid crystal phases of the polar molecule DB9ONO2 display fluctuations on two incommensurate and temperature dependent length scales. We have used high resolution X-ray scattering to study the structure of this material between 80 °C and 230 °C at atmospheric pressure. We confirm the previously reported phase sequence of multiply reentrant nematic phases. The low temperature nematic phases are highly ordered, with correlation lengths exceeding 3 300 A far from the phase boundary. We find evidence of an S c phase between the low temperature SA1 and Sc phases.Les phases cristal liquide de la molécule polaire DB9ONO 2 montrent des fluctuations selon deux échelles incommensurables et dépendantes de la température. Nous avons utilisé la diffusion des rayons X à haute résolution pour étudier la structure de ce matériau entre 80 °C et 230 °C à la pression atmosphérique. Nous confirmons la séquence de phases nématiques réentrantes multiples qui avait été annoncée précédemment. Les phases nématiques à basse température sont très ordonnées, avec des longueurs de corrélation qui dépassent 3 300 A loin de la limite de phase. Nous trouvons également une phase Sc entre les phases basse température SA1 et Sc

Formation of a hexagonal columnar mesophase by N-acylated Poly(ethylenimine)

Both discotic molecules and certain linear polymers form columnar hexagonal mesophases. Whereas the dislike structure of the macrocycle 1 is dictated by the molecular shape, in polymer 2 it is presumably enforced by a helical folding of the polymer's main chain induced by the side chains (bottom right)