A time-dependent density functional theory scheme for efficient calculations of dynamic (hyper)polarizabilities

We present an efficient perturbative method to obtain both static and dynamic polarizabilities and hyperpolarizabilities of complex electronic systems. This approach is based on the solution of a frequency dependent Sternheimer equation, within the formalism of time-dependent density functional theory, and allows the calculation of the response both in resonance and out of resonance. Furthermore, the excellent scaling with the number of atoms opens the way to the investigation of response properties of very large molecular systems. To demonstrate the capabilities of this method, we implemented it in a real-space (basis-set free) code, and applied it to benchmark molecules, namely CO, H2O, and paranitroaniline (PNA). Our results are in agreement with experimental and previous theoretical studies, and fully validate our approach.Comment: 9 pages, 4 figure

Alloying effects on the optical properties of Ge1−x_{1-x}Six_x nanocrystals from TDDFT and comparison with effective-medium theory

We present the optical spectra of Ge$_{1-x}$Si$_x$ alloy nanocrystals calculated with time-dependent density-functional theory in the adiabatic local-density ap proximation (TDLDA). The spectra change smoothly as a function of the compositio n $x$. On the Ge side of the composition range, the lowest excitations at the ab sorption edge are almost pure Kohn-Sham independent-particle HOMO-LUMO transitio ns, while for higher Si contents strong mixing of transitions is found. Within T DLDA the first peak is slightly higher in energy than in earlier independent-par ticle calculations. However, the absorption onset and in particular its composit ion dependence is similar to independent-particle results. Moreover, classical depolarization effects are responsible for a very strong suppression of the abs orption intensity. We show that they can be taken into account in a simpler way using Maxwell-Garnett classical effective-medium theory. Emission spectra are in vestigated by calculating the absorption of excited nanocrystals at their relaxe d geometry. The structural contribution to the Stokes shift is about 0.5 eV. Th e decomposition of the emission spectra in terms of independent-particle transit ions is similar to what is found for absorption. For the emission, very weak tra nsitions are found in Ge-rich clusters well below the strong absorption onset.Comment: submitted to Phys. Rev.

On the calculation of the bandgap of periodic solids with MGGA functionals using the total energy

During the last few years, it has become more and more clear that functionals of the meta generalized gradient approximation (MGGA) are more accurate than GGA functionals for the geometry and energetics of electronic systems. However, MGGA functionals are also potentially more interesting for the electronic structure, in particular, when the potential is nonmultiplicative (i.e., when MGGAs are implemented in the generalized Kohn-Sham framework), which may help to get more accurate bandgaps. Here, we show that the calculation of bandgap of solids with MGGA functionals can also be done very accurately in a non-self-consistent manner. This scheme uses only the total energy and can, therefore, be very useful when the self-consistent implementation of a particular MGGA functional is not available. Since self-consistent MGGA calculations may be difficult to converge, the non-self-consistent scheme may also help to speed up the calculations. Furthermore, it can be applied to any other types of functionals, for which the implementation of the corresponding potential is not trivial

Efficient calculation of van der Waals dispersion coefficients with time-dependent density functional theory in real time: application to polycyclic aromatic hydrocarbons

The van der Waals dispersion coefficients of a set of polycyclic aromatic hydrocarbons, ranging in size from the single-cycle benzene to circumovalene (C66H20), are calculated with a real-time propagation approach to time-dependent density functional theory (TDDFT). In the non-retarded regime, the Casimir-Polder integral is employed to obtain C6, once the dynamic polarizabilities have been computed at imaginary frequencies with TDDFT. On the other hand, the numerical coefficient that characterizes the fully retarded regime is obtained from the static polarizabilities. This ab initio strategy has favorable scaling with the size of the system - as demonstrated by the size of the reported molecules - and can be easily extended to obtain higher order van der Waals coefficients.Comment: submitted to J. Chem. Phy

SPARC is a new myeloid-derived suppressor cell marker licensing suppressive activities

Myeloid-derived suppressor cells (MDSC) are well-known key negative regulators of the immune response during tumor growth, however scattered is the knowledge of their capacity to influence and adapt to the different tumor microenvironments and of the markers that identify those capacities. Here we show that the secreted protein acidic and rich in cysteine (SPARC) identifies in both human and mouse MDSC with immune suppressive capacity and pro-tumoral activities including the induction of epithelial-to-mesenchymal transition (EMT) and angiogenesis. In mice the genetic deletion of SPARC reduced MDSC immune suppression and reverted EMT. Sparc−/− MDSC were less suppressive overall and the granulocytic fraction was more prone to extrude neutrophil extracellular traps (NET). Surprisingly, arginase-I and NOS2, whose expression can be controlled by STAT3, were not down-regulated in Sparc−/− MDSC, although less suppressive than wild type (WT) counterpart. Flow cytometry analysis showed equal phosphorylation of STAT3 but reduced ROS production that was associated with reduced nuclear translocation of the NF-kB p50 subunit in Sparc−/− than WT MDSC. The limited p50 in nuclei reduce the formation of the immunosuppressive p50:p50 homodimers in favor of the p65:p50 inflammatory heterodimers. Supporting this hypothesis, the production of TNF by Sparc−/− MDSC was significantly higher than by WT MDSC. Although associated with tumor-induced chronic inflammation, TNF, if produced at high doses, becomes a key factor in mediating tumor rejection. Therefore, it is foreseeable that an unbalance in TNF production could skew MDSC toward an inflammatory, anti-tumor phenotype. Notably, TNF is also required for inflammation-driven NETosis. The high level of TNF in Sparc−/− MDSC might explain their increased spontaneous NET formation as that we detected both in vitro and in vivo, in association with signs of endothelial damage. We propose SPARC as a new potential marker of MDSC, in both human and mouse, with the additional feature of controlling MDSC suppressive activity while preventing an excessive inflammatory state through the control of NF-kB signaling pathway

ON THE APPLICATION OF REMOTE SENSING TIME SERIES ANALYSIS FOR LAND COVER MAPPING: SPECTRAL INDICES FOR CROPS CLASSIFICATION

Abstract. This study aims to introduce a semi-automatic classification workflow for the production of a land use/land cover (LULC) map of the island of Sardinia (Italy) following the CORINE legend schema, and a ground spatial resolution compatible with a scale of 1:25.000. The classification is based on free high-resolution satellite imagery from Sentinel-1 and Sentinel-2 collected in 2020, ancillary data derived from Sardinian Geoportal, Joint Research Centre (JRC) and OpenStreetMap. The LULC map production includes three steps: 1) pixel-based classification, realized with two different approaches, that use i) information derived from existing thematic maps eventually re-coded in case of incoherencies observed between datasets and/or satellite data products, and ii) spectral indices and parameter thresholds defined on the basis of multitemporal analysis; 2) segmentation of Sentinel-1 and 2 annual composites, and pre-labelling of segments with the pixel-based classified map, obtaining the preliminary map; 3) visual inspection procedure in order to confirm, or re-assign, classes to polygons. The accuracy of the preliminary map was tested in a sample area and on specific class of non-irrigated crops through ground truth data collected from a detailed photo-interpretation, estimating 97% of overall accuracy. The results show a great improvement from existing thematic maps in terms of detail, with the possibility of a yearly updating of the map via automatic processes. However, some limitations were found, due to the high fragmentation of Sardinian landscape and the high variety of crop types and agricultural practices, that could affect the efficiency of the classifier

The Dynamics of Aqueous Hydroxide Ion Transport Probed via Ultrafast Vibrational Echo Experiments

Paper presented at the Sixteenth International Conference on Ultrafast Phenomena.We use peakshift, transient grating, and 2D IR measurements to probe the dynamics of NaOD solutions. Our experiments suggest that OD- possesses a stable solvation shell and signatures of fast intermolecular proton transfer are observed

Seeking and Avoiding Choice Closure to Enhance Outcome Satisfaction

Consumers gain choice closure when they perceive a sense of finality over a past decision and limit comparisons between the selected and the forgone options. We investigate consumers’ ability to make strategic use of choice closure to enhance outcome satisfaction. Seven studies show that consumers experience greater satisfaction when they achieve choice closure with an inferior outcome and when they do not achieve choice closure with a superior outcome; however, they expect to be more satisfied by avoiding choice closure with an inferior outcome and by seeking it with a superior outcome. We provide a rationale for this experience–expectation contrast based on rule overgeneralization. Consumers form their expectation on an implicit rule learned and internalized in a context in which it is appropriate and advantageous: when they aim to increase satisfaction with a future choice; however, consumers erroneously apply the same implicit rule to a different context, one in which they aim to increase satisfaction with a past choice. We conclude that consumers are unlikely to be able to make strategic use of choice closure to enhance satisfaction with the outcome of a decision they have made

A Joint Account With My Future Self: Self-Continuity Facilitates Adjustment of Present Spending to Future Income Changes

Is consumers’ present spending influenced by future changes in their income? From an economic perspective, consumers should reduce present spending when anticipating a future income decrease and boost spending when anticipating a future income increase to maximize their welfare. We find that although consumers tend to adjust their spending to a future income decrease, they are less likely to do so to a future income increase. We show that this is in part due to a low sense of self-continuity, a tendency to view the future self whose income increases as if it were a different person and, as a result, to categorize present and future income into two separate mental accounts. Enhancing self-continuity leads consumers to combine present and future income in a single mental account, and thereby facilitates adjustment of present spending to a future income increase. Whereas prior work linked high self-continuity to reduced present spending, we identify a context in which high self-continuity can boost present spending. We discuss the implications of these findings for consumer well-being