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Proc Natl Acad Sci U S A ; 108(23): 9342-5, 2011 Jun 07.
Artigo em Inglês | MEDLINE | ID: mdl-21597000


Many physical and chemical properties of the light rare-earths and actinides are governed by the active role of f electrons, and despite intensive efforts the details of the mechanisms of phase stability and transformation are not fully understood. A prominent example which has attracted a lot of interest, both experimentally and theoretically over the years is the isostructural γ - α transition in cerium. We have determined by inelastic X-ray scattering, the complete phonon dispersion scheme of elemental cerium across the γ → α transition, and compared it with theoretical results using ab initio lattice dynamics. Several phonon branches show strong changes in the dispersion shape, indicating large modifications in the interactions between phonons and conduction electrons. This is reflected as well by the lattice Grüneisen parameters, particularly around the X point. We derive a vibrational entropy change ΔS(γ-α)(vib) ≈ (0.33+/-0.03)k(B), illustrating the importance of the lattice contribution to the transition. Additionally, we compare first principles calculations with the experiments to shed light on the mechanism underlying the isostructural volume collapse in cerium under pressure.

Cério/química , Fenômenos Químicos , Modelos Químicos , Algoritmos , Cinética , Espalhamento a Baixo Ângulo , Difração de Raios X/métodos
Proc Natl Acad Sci U S A ; 103(21): 7962-7, 2006 May 23.
Artigo em Inglês | MEDLINE | ID: mdl-16690742


Current understanding of electrostatics in water is based on mean-field theories like the Poisson-Boltzmann formalism and its approximations, which are routinely used in colloid science and computational biology. This approach, however, breaks down for highly charged systems, which exhibit counterintuitive phenomena such as overcharging and like-charge attraction. Models of counterion correlations have been proposed as possible explanations, but no experimental comparisons are available. Here, collective dynamics of counterions that mediate like-charge attraction between F-actin filaments have been directly observed in aqueous solution using high-resolution inelastic x-ray scattering down to molecular length-scales. We find a previously undescribed acoustic-like phonon mode associated with correlated counterions. The excitation spectra at high wave-vector Q reveal unexpected dynamics due to ions interacting with their "cages" of nearest neighbors. We examine this behavior in the context of intrinsic charge density variations on F-actin. The measured speed of sound and collective relaxation rates in this liquid agree surprisingly well with simple model calculations.

Físico-Química/métodos , Polímeros , Actinas/química , Biofísica/métodos , Biopolímeros , Eletrólitos , Íons , Modelos Moleculares , Espalhamento de Radiação , Eletricidade Estática , Raios X
Phys Rev Lett ; 96(11): 115502, 2006 Mar 24.
Artigo em Inglês | MEDLINE | ID: mdl-16605838


We have determined the lattice dynamics of molybdenum at high pressure to 37 GPa using high-resolution inelastic x-ray scattering. Over the investigated pressure range, we find a significant decrease in the H-point phonon anomaly. We also present calculations based on density functional theory that accurately predict this pressure dependence. Based on these results, we infer that the likely explanation for the H-point anomaly in molybdenum is strong electron-phonon coupling, which decreases upon compression due to the shift of the Fermi level with respect to the relevant electronic bands.

Phys Rev Lett ; 96(3): 035507, 2006 Jan 27.
Artigo em Inglês | MEDLINE | ID: mdl-16486728


The longitudinal acoustic and optical phonon branches along the Gamma-X direction of MgO at 35 GPa have been determined by inelastic x-ray scattering using synchrotron radiation and a diamond-anvil cell. The experimentally observed phonon branches are in remarkable agreement with ab initio lattice dynamics results. The derived thermodynamic properties, such as the specific heat CV and the entropy S are in very good accord with values obtained from a thermodynamically assessed data set involving measured data on molar volume, heat capacity at constant pressure, bulk modulus and thermal expansion.