Vibrational spectroscopies in liquid water: on temperature and coordination effects in Raman and infrared spectroscopies

Water is an ubiquitous liquid that has several exotic and anomalous properties. Despite its apparent simple chemical formula, its capability of forming a dynamic network of hydrogen bonds leads to a rich variety of physics. Here we study the vibrations of water using molecular dynamics simulations, mainly concentrating on the Raman and infrared spectroscopic signatures. We investigate the consequences of the temperature on the vibrational frequencies, and we enter the details of the hydrogen bonding coordination by using restrained simulations in order to gain quantitative insight on the dependence of the frequencies on the neighbouring molecules. Further we consider the differences due to the different methods of solving the electronic structure to evaluate the forces on the ions, and report results on the angular correlations, isotopic mixtures HOD in H$_2$O/D$_2$O and and the dielectric constants in water.Comment: 15 pages, 7 figures, 5 table

A NMR and molecular dynamics study of CO2-bearing basaltic melts and glasses

International audienceThe presence of volatile, especially carbon dioxide (CO2), in silicate liquids is considered as a key parameter to magmatic degassing and eruptive processes. Unfortunately, due to experimental difficulties, our current knowledge on the CO2 effect on silicate melt structure is weak and relies on the observation of ex-situ recovered CO2-bearing glasses.In the present work, we confront the results obtained from NMR spectroscopic observations of glass synthesised at pressure between 0.5 and 3.0 GPa and theoretical investigations from first-principles molecular dynamics (FPMD) simulations conducted at 5.0 and 8.0 GPa on high temperature melt for a simplified basaltic composition.The results obtained on the aluminosilicate framework (molar fraction of silicon species and Al average coordination number) suggest that both ex-situ and in-situ results compare adequately. The results are in agreement with our current knowledge on the change in aluminosilicate melt/glass structure with changing intensive conditions. Increasing pressure from 0.5 to 8.0 GPa induces 1) an increase in the average Al coordination number from 4.1 to almost 5.0 and 2) an increase in the degree of polymerisation with NBO/Si changing from 1.30 to 0.80.The presence of CO2 does not seem to induce a dramatic change on both the average Al coordination number and the NBO/Si. FPMD simulations performed with 0 and 20 wt.% CO2 at 8.0 GPa result in a change from 4.84 to 4.96 for the average Al coordination number and in a change from 0.87 to 0.80 for the NBO/Si value, respectively.On the contrary, there is a lack of consistency in between the CO2 speciation obtained from NMR spectroscopy and from FPMD simulations. Whereas the analysis of glasses does not reveal the presence of CO2mol species, the FPMD simulation results suggests the existence of a small proportion of CO2mol. Further work with in-situ experimental approach is therefore required to explain the observed lack of consistency between the CO2 speciation in glass and in high temperature melt with basaltic composition

Molecular hydrodynamics from memory kernels

The memory kernel for a tagged particle in a fluid, computed from molecular dynamics simulations, decays algebraically as t−3/2. We show how the hydrodynamic Basset-Boussinesq force naturally emerges from this long-time tail and generalize the concept of hydrodynamic added mass. This mass term is negative in the present case of a molecular solute, which is at odds with incompressible hydrodynamics predictions. Lastly, we discuss the various contributions to the friction, the associated time scales, and the crossover between the molecular and hydrodynamic regimes upon increasing the solute radius

Determination of Strong-Interaction Widths and Shifts of Pionic X-Rays with a Crystal Spectrometer

Pionic 3d-2p atomic transitions in F, Na, and Mg have been studied using a bent crystal spectrometer. The pionic atoms were formed in the production target placed in the external proton beam of the Space Radiation Effects Laboratory synchrocyclotron. The observed energies and widths of the transitions are E=41679(3) eV and Γ=21(8) eV, E=62434(18) eV and Γ=22(80) eV, E=74389(9) eV and Γ=67(35) eV, in F, Na, and Mg, respectively. The results are compared with calculations based on a pion-nucleus optical potential

Enhanced Processing of Threat Stimuli under Limited Attentional Resources

The ability to process stimuli that convey potential threat, under conditions of limited attentional resources, confers adaptive advantages. This study examined the neurobiology underpinnings of this capacity. Employing an attentional blink paradigm, in conjunction with functional magnetic resonance imaging, we manipulated the salience of the second of 2 face target stimuli (T2), by varying emotionality. Behaviorally, fearful T2 faces were identified significantly more than neutral faces. Activity in fusiform face area increased with correct identification of T2 faces. Enhanced activity in rostral anterior cingulate cortex (rACC) accounted for the benefit in detection of fearful stimuli reflected in a significant interaction between target valence and correct identification. Thus, under conditions of limited attention resources activation in rACC correlated with enhanced processing of emotional stimuli. We suggest that these data support a model in which a prefrontal “gate” mechanism controls conscious access of emotional information under conditions of limited attentional resources

Sub MeV Particles Detection and Identification in the MUNU detector ((1)ISN, IN2P3/CNRS-UJF, Grenoble, France, (2)Institut de Physique, Neuch\^atel, Switzerland, (3) INFN, Padova Italy, (4) Physik-Institut, Z\"{u}rich, Switzerland)

We report on the performance of a 1 m$^{3}$ TPC filled with CF$_{4}$ at 3 bar, immersed in liquid scintillator and viewed by photomultipliers. Particle detection, event identification and localization achieved by measuring both the current signal and the scintillation light are presented. Particular features of $\alpha$ particle detection are also discussed. Finally, the ${54}$Mn photopeak, reconstructed from the Compton scattering and recoil angle is shown.Comment: Latex, 19 pages, 20 figure