Thermodynamics of Na_8 and Na_{20} clusters studied with ab-initio electronic structure methods

We study the thermodynamics of Na_8 and Na_{20} clusters using multiple-histogram methods and an ab initio treatment of the valence electrons within density functional theory. We consider the influence of various electron kinetic-energy functionals and pseudopotentials on the canonical ionic specific heats. The results for all models we consider show qualitative similarities, but also significant temperature shifts from model to model of peaks and other features in the specific-heat curves. The use of phenomenological pseudopotentials shifts the melting peak substantially (~ 50--100 K) when compared to ab-initio results. It is argued that the choice of a good pseudopotential and use of better electronic kinetic-energy functionals has the potential for performing large time scale and large sized thermodynamical simulations on clusters.Comment: LaTeX file and EPS figures. 24 pages, 13 figures. Submitted to Phys. Rev.

Ionic and electronic structure of sodium clusters up to N=59

We determined the ionic and electronic structure of sodium clusters with even electron numbers and 2 to 59 atoms in axially averaged and three-dimensional density functional calculations. A local, phenomenological pseudopotential that reproduces important bulk and atomic properties and facilitates structure calculations has been developed. Photoabsorption spectra have been calculated for $\mathrm{Na}_2$, $\mathrm{Na}_8$, and $\mathrm{Na}_9^+$ to $\mathrm{Na}_{59}^+$. The consistent inclusion of ionic structure considerably improves agreement with experiment. An icosahedral growth pattern is observed for $\mathrm{Na}_{19}^+$ to $\mathrm{Na}_{59}^+$. This finding is supported by photoabsorption data.Comment: To appear in Phys. Rev. B 62. Version with figures in better quality can be requested from the author

Recommendations for obtaining unbiased chlorophyll estimates from in situ chlorophyll fluorometers: A global analysis of WET Labs ECO sensors

Chlorophyll fluorometers provide the largest in situ global data set for estimating phytoplankton biomass because of their ease of use, size, power consumption, and relatively low price. While in situ chlorophyll a (Chl) fluorescence is proxy for Chl a concentration, and hence phytoplankton biomass, there exist large natural variations in the relationship between in situ fluorescence and extracted Chl a concentration. Despite this large natural variability, we present here a global validation data set for the WET Labs Environmental Characterization Optics (ECO) series chlorophyll fluorometers that suggests a factor of 2 overestimation in the factory calibrated Chl a estimates for this specific manufacturer and series of sensors. We base these results on paired High Pressure Liquid Chromatography (HPLC) and in situ fluorescence match ups for which non-photochemically quenched fluorescence observations were removed. Additionally, we examined matches between the factory-calibrated in situ fluorescence and estimates of chlorophyll concentration determined from in situ radiometry, absorption line height, NASA’s standard ocean color algorithm as well as laboratory calibrations with phytoplankton monocultures spanning diverse species that support the factor of 2 bias. We therefore recommend the factor of 2 global bias correction be applied for the WET Labs ECO sensors, at the user level, to improve the global accuracy of chlorophyll concentration estimates and products derived from them. We recommend that other fluorometer makes and models should likewise undergo global analyses to identify potential bias in factory calibration

Thermal expansion in small metal clusters and its impact on the electric polarizability

The thermal expansion coefficients of $\mathrm{Na}_{N}$ clusters with $8 \le N \le 40$ and $\mathrm{Al}_{7}$, $\mathrm{Al}_{13}^-$ and $\mathrm{Al}_{14}^-$ are obtained from {\it ab initio} Born-Oppenheimer LDA molecular dynamics. Thermal expansion of small metal clusters is considerably larger than that in the bulk and size-dependent. We demonstrate that the average static electric dipole polarizability of Na clusters depends linearly on the mean interatomic distance and only to a minor extent on the detailed ionic configuration when the overall shape of the electron density is enforced by electronic shell effects. The polarizability is thus a sensitive indicator for thermal expansion. We show that taking this effect into account brings theoretical and experimental polarizabilities into quantitative agreement.Comment: 4 pages, 2 figures, one table. Accepted for publication in Physical Review Letters. References 10 and 23 update

Ionic structure and photoabsorption in medium sized sodium clusters

We present ground-state configurations and photoabsorption spectra of Na-7+, Na-27+ and Na-41+. Both the ionic structure and the photoabsorption spectra of medium-size sodium clusters beyond Na-20 have been calculated self-consistently with a nonspherical treatment of the valence electrons in density functional theory. We use a local pseudopotential that has been adjusted to experimental bulk properties and the atomic 3s level of sodium. Our studies have shown that both the ionic structure of the ground state and the positions of the plasmon resonances depend sensitively on the pseudopotential used in the calculation, which stresses the importance of its consistent use in both steps.Comment: 4 pages, 3 figures. Accepted for publication in PRB, tentatively July 15th, 1998 some typos corrected, brought to nicer forma

The chlorophyll seasonal dynamics in the Black Sea as inferred from Biogeochemical-Argo floats

Biogeochemical-Argo (BGC-Argo) floats offer the opportunity to investigate the spatial and temporal dynamics of chlorophyll a (Chla) profiles. In the Black Sea, the unusual abundance of colored dissolved organic matter (CDOM) and the absence of oxygen below ∼80-100m require a revision of the classic formulation used to link the fluorescence signal and the algal chlorophyll concentration (e.g. Xing et al., 2017). Indeed, the very high content of CDOM in the basin is thought to be responsible for the apparent increase of Chla concentrations at depth, where it should be zero due to the absence of light. Here, the classic formulation to link fluorescence and Chla is revised based on a reference Chla dataset sampled during a scientific cruise onboard RV Akademik and analysed with High Performance Liquid Chromatography (HPLC). Then, using the established equation to remove the contribution of CDOM to the fluorescence signal, we estimated the Chla profiles from 4 BGC-Argo floats during the period 2014-2017. All Chla profiles were thus highly quality controlled by using the Argo documentation (Schmechtig et al., 2015). Especially, we removed bad data (e.g. spikes, outliers) and we corrected the Non-Photochemical Quenching effect, a photoprotective mechanism resulting in a decrease in the fluorescence signal at the surface. The Chla profiles are categorized based on fitting algorithms (e.g. sigmoid, exponential, gaussian) and empirical criteria. They display a large variety of shapes across the seasons (e.g. homogeneity in the mixed layer, subsurface maximum, double peaks below the surface, etc.) with roughly homogeneous profiles dominating between November and February while subsurface maxima are present during the rest of the year, with in summer a clearly-marked deep chlorophyll maximum (DCM). We then investigate the formation mechanism of DCMs based on the hysteresis hypothesis for the temperate ocean proposed by Navarro et al., (2013). For this, we looked at the correlation between the position of DCMs and the potential density anomaly of the mixed layer when it is maximum in winter, usually between February and March. We show that DCMs are highly correlated with the potential density anomaly of the previous winter mixed layer where a winter bloom initiated while the correlation with the 10% and 1% light levels is poor. This is in agreement with the hysteresis hypothesis that assumes that in regions where a bloom forms in late winter/early spring, this bloom remains established at a fixed density (i.e. the density of the mixed layer when it is maximum) until the end of summer acting as a barrier for the diffusion of nutrients from below and preventing the occurrence of deeper blooms due to a shading effect. This bloom is finally progressively eroded in autumn, when the depth of the mixed layer increases again

A BGC-Argo Guide: Planning, Deployment, Data Handling and Usage

The Biogeochemical-Argo program (BGC-Argo) is a new profiling-float-based, ocean wide, and distributed ocean monitoring program which is tightly linked to, and has benefited significantly from, the Argo program. The community has recommended for BGC-Argo to measure six additional properties in addition to pressure, temperature and salinity measured by Argo, to include oxygen, pH, nitrate, downwelling light, chlorophyll fluorescenceandtheopticalbackscatteringcoefficient.Thepurposeofthisadditionisto enable the monitoring of ocean biogeochemistry and health, and in particular, monitor major processes such as ocean deoxygenation, acidification and warming and their effect on phytoplankton, the main source of energy of marine ecosystems. Here we describe the salient issues associated with the operation of the BGC-Argo network, with information useful for those interested in deploying floats and using the data they produce. The topics include float testing, deployment and increasingly, recovery. Aspects of data management, processing and quality control are covered as well as specific issues associated with each of the six BGC-Argo sensors. In particular, it is recommended that water samples be collected during float deployment to be used for validation of sensor output

Chimie théorique : les défis d'une filière de formation à faibles effectifs

International audienceEn cette année où le prix Nobel de Chimie a récompensé trois éminents chimistes théoriciens, dont Martin Karplus de l'Université de Strasbourg, ce champ disciplinaire, la Chimie théorique, vit un paradoxe. Comme l'illustrent plusieurs articles de ce numéro spécial de l'Actualité Chimique, elle reste un point central dans le développement de nouvelles connaissances fondamentales et apporte un éclairage précieux sur de nombreux travaux expérimentaux ; elle délivre représentation et interprétation des phénomènes à l'échelle moléculaire ; elle s'adapte à la puissance des outils numériques actuels ; des développements méthodologiques permanents permettent de repousser les limites de son applicabilité, aussi bien en termes de dimension des systèmes étudiés que de leur complexité physico-chimique. Il n'est pratiquement pas de structure de recherche, académique ou industrielle, qui n'ait en son sein une équipe de modélisation-simulation. Les besoins en experts qualifiés en la matière ne cessent de progresser, compte tenu du nombre croissant de sujets de recherche requérant d'une part de savoir utiliser avec recul et esprit critique les nombreux logiciels conviviaux et robustes disponibles et d'autre part de savoir construire des modèles théoriques capturant l'essence de la complexité expérimentale

Chimie théorique : les défis d'une filière de formation à faibles effectifs

International audienceEn cette année où le prix Nobel de Chimie a récompensé trois éminents chimistes théoriciens, dont Martin Karplus de l'Université de Strasbourg, ce champ disciplinaire, la Chimie théorique, vit un paradoxe. Comme l'illustrent plusieurs articles de ce numéro spécial de l'Actualité Chimique, elle reste un point central dans le développement de nouvelles connaissances fondamentales et apporte un éclairage précieux sur de nombreux travaux expérimentaux ; elle délivre représentation et interprétation des phénomènes à l'échelle moléculaire ; elle s'adapte à la puissance des outils numériques actuels ; des développements méthodologiques permanents permettent de repousser les limites de son applicabilité, aussi bien en termes de dimension des systèmes étudiés que de leur complexité physico-chimique. Il n'est pratiquement pas de structure de recherche, académique ou industrielle, qui n'ait en son sein une équipe de modélisation-simulation. Les besoins en experts qualifiés en la matière ne cessent de progresser, compte tenu du nombre croissant de sujets de recherche requérant d'une part de savoir utiliser avec recul et esprit critique les nombreux logiciels conviviaux et robustes disponibles et d'autre part de savoir construire des modèles théoriques capturant l'essence de la complexité expérimentale