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Bacchus-Montabonel M.-C.,University Claude Bernard Lyon 1 | Calvo F.,Laboratoire Interdisciplinaire Of Physique
Physical Chemistry Chemical Physics | Year: 2015

Stepwise hydration of uracil has been theoretically revisited using different methods ranging from classical force fields to quantum chemical approaches. Hydration initially begins within the uracil plane but proceeds at four molecules into three-dimensional configurations or even water clusters next to the nucleobase. The relative stability between the various structures is significantly affected by zero-point energy and finite temperature (entropy) effects and also gives rise to markedly different responses to an excitation by an impinging high-energy proton. In particular, charge transfer to the molecular complex is dramatically altered in collisions toward the coating cluster but barely modified for peripheral hydration patterns. This journal is © the Owner Societies.

Berti S.,Laboratoire Interdisciplinaire Of Physique | Berti S.,Laboratoire Of Me Teorologie Dynamique | Dos Santos F.A.,PROOCEANO Servicxo Oceanografico | Lacorata G.,National Research Council Italy | Vulpiani A.,University of Rome La Sapienza
Journal of Physical Oceanography | Year: 2011

In the framework of Monitoring by Ocean Drifters (MONDO) project, a set of Lagrangian drifters were released in proximity of the Brazil Current, the western branch of the subtropical gyre in the South Atlantic Ocean. The experimental strategy of deploying part of the buoys in clusters offers the opportunity to examine relative dispersion on a wide range of scales. Adopting a dynamical systems approach, the authors focus their attention on scale-dependent indicators, like the finite-scale Lyapunov exponent (FSLE) and the finite-scale (mean square) relative velocity (FSRV) between two drifters as a function of their separation and compare them with classic time-dependent statistical quantities like the mean-square relative displacement between two drifters and the effective diffusivity as functions of the time lag from the release. The authors find that, dependently on the given observable, the quasigeostrophic turbulence scenario is overall compatible with their data analysis, with discrepancies from the expected behavior of 2D turbulent trajectories likely to be ascribed to the nonstationary and nonhomogeneous characteristics of the flow, as well as to possible ageostrophic effects. Submesoscale features of;O(1) km are considered to play a role, to some extent, in determining the properties of relative dispersion as well as the shape of the energy spectrum. The authors also present numerical simulations of an ocean general circulation model (OGCM) of the South Atlantic and discuss the comparison between experimental and model data about mesoscale dispersion. © 2011 American Meteorological Society.

Calvo F.,Laboratoire Interdisciplinaire Of Physique
AIP Conference Proceedings | Year: 2015

Alkali impurities bind to helium nanodroplets very differently depending on their size and charge state, large neutral or charged dopants being wetted by the droplet whereas small neutral impurities prefer to reside aside. Using various computational modeling tools such as quantum Monte Carlo and path-integral molecular dynamics simulations, we have revisited some aspects of the physical chemistry of helium droplets interacting with sodium impurities, including the onset of snowball formation in presence of many-body polarization forces, the transition from non-wetted to wetted behavior in larger sodium clusters, and the kinetics of submersion of small dopants after sudden ionization. © 2015 AIP Publishing LLC.

Hernandez-Rojas J.,University of La Laguna | Calvo F.,Laboratoire Interdisciplinaire Of Physique | Noya E.G.,CSIC - Institute of Physical Chemistry "Rocasolano"
Journal of Chemical Theory and Computation | Year: 2015

The semiclassical method of quantum thermal baths by colored noise thermostats has been used to simulate various atomic systems in the molecular and bulk limits, at finite temperature and in moderately to strongly anharmonic regimes. In all cases, the method performs relatively well against alternative approaches in predicting correct energetic properties, including in the presence of phase changes, provided that vibrational delocalization is not too strong-neon appearing already as an upper limiting case. In contrast, the dynamical behavior inferred from global indicators such as the root-mean-square bond length fluctuation index or the vibrational spectrum reveals more marked differences caused by zero-point energy leakage, except in the case of isolated molecules with well separated vibrational modes. To correct for such deficiencies and reduce the undesired transfer among modes, empirical modifications of the noise power spectral density were attempted to better describe thermal equilibrium but still failed when used as semiclassical preparation for microcanonical trajectories. © 2015 American Chemical Society.

Calvo F.,Laboratoire Interdisciplinaire Of Physique | Li Y.,Catholic University of Leuven | Kiawi D.M.,Radboud University Nijmegen | Kiawi D.M.,University of Amsterdam | And 3 more authors.
Physical Chemistry Chemical Physics | Year: 2015

For structural assignment of gas phase compounds, infrared action spectra are usually compared to computed linear absorption spectra. However, action spectroscopy is highly nonlinear owing to the necessary transfer of the excitation energy and its subsequent redistribution leading to statistical ionization or dissociation. Here, we examine by joint experiment and dedicated modeling how such nonlinear effects affect the spectroscopic features in the case of selected inorganic clusters. Vibrational spectra of neutral silicon clusters are recorded by tunable IR-UV two-color ionization while IR spectra for cationic vanadium oxide clusters are obtained by IR multiphoton absorption followed by dissociation of the bare cluster or of its complex with Xe. Our kinetic modeling accounts for vibrational anharmonicities, for the laser interaction through photon absorption and stimulated emission rates, as well as for the relevant ionization or dissociation rates, all based on input parameters from quantum chemical calculations. Comparison of the measured and calculated spectra indicates an overall agreement as far as trends are concerned, except for the photodissociation of the V3O7+-Xe messenger complex, for which anharmonicities are too large and poorly captured by the perturbative anharmonic model. In all systems studied, nonlinear effects are essentially manifested by variations in the intensities as well as spectral broadenings. Differences in some band positions originate from inaccuracies of the quantum chemical data rather than specific nonlinear effects. The simulations further yield information on the average number of photons absorbed, which is otherwise unaccessible information: several to several tens of photons need to be absorbed to observe a band through dissociation, while three to five photons can be sufficient for detection of a band via IR-UV ionization. This journal is © the Owner Societies.

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