Photo-excitation of a light-harvesting supra-molecular triad: a Time-Dependent DFT study

We present the first time-dependent density-functional theory (TDDFT) calculation on a light harvesting triad carotenoid-diaryl-porphyrin-C60. Besides the numerical challenge that the ab initio study of the electronic structure of such a large system presents, we show that TDDFT is able to provide an accurate description of the excited state properties of the system. In particular we calculate the photo-absorption spectrum of the supra-molecular assembly, and we provide an interpretation of the photo-excitation mechanism in terms of the properties of the component moieties. The spectrum is in good agreement with experimental data, and provides useful insight on the photo-induced charge transfer mechanism which characterizes the system.Comment: Accepted for publication on JPC, March 09th 200

Quantum coherence controls the charge separation in a prototypical artificial light harvesting system

In artificial light harvesting systems the conversion of light into charges or chemical energy happens on the femtosecond time scale and is thought to involve the incoherent jump of an electron from the optical absorber to an electron acceptor. Here we investigate the primary process of electronic charge transfer dynamics in a carotene-porphyrin-fullerene triad, a prototypical elementary component for an artificial light harvesting system combining coherent femtosecond spectroscopy and first-principles quantum dynamics simulations. Our experimental and theoretical results provide strong evidence that the driving mechanism of the photoinduced current generation cycle is a quantum-correlated wavelike motion of electrons and nuclei on a timescale of few tens of femtoseconds. We furthermore highlight the fundamental role played by the interface between the light-absorbing chromophore and the charge acceptor in triggering the coherent wavelike electron-hole splitting. © 2013 IEEE

Mouthiers-sur-Boëme, Chez les Rois

Chez les Rois est un gisement de référence de l'Aurignacien charentais et un des rares gisements aurignaciens européens à avoir livré des restes humains en place. Fouillé entre 1930 et 1939 par Potut et entre 1948 et 1952 par Mouton et Joffroy (1958), ce gisement a fait l'objet d'un sondage en 2005 et d'une fouille programmée entre 2006 et 2008 (d'Errico et Vanhaeren 2005, 2006, 2007, 2008). Cette opération de terrain a fait suite à la reprise de l'étude des restes humains et du matériel archéologique issus des fouilles Mouton et Joffroy ainsi qu'à sa datation (Ramirez Rozzi et al. sous presse). L'objectif des nouvelles fouilles était de préciser l'attribution culturelle des assemblages, la chronologie et nature de l'occupation aurignacienne ainsi que l'affiliation taxinomique des groupes humains qui ont fréquenté le site

Embedded, micro-interdigitated flow fields in high areal-loading intercalation electrodes towards seawater desalination and beyond

Faradaic deionization (FDI) is a promising technology for energy-efficient water desalination using porous electrodes containing redox-active materials. Herein, we demonstrate for the first time the capability of a symmetric FDI flow cell to produce freshwater (<17.1 mM NaCl) from concentrated brackish water (118mM), to produce effluent near freshwater salinity (19.1 mM) from influent with seawater-level salinity (496 mM), and to reduce the salinity of hypersaline brine from 781 mM to 227 mM. These remarkable salt-removal levels were enabled by using flow-through electrodes with high areal-loading of nickel hexacyanoferrate (NiHCF) Prussian Blue analogue intercalation material. The pumping energy consumption due to flow-through electrodes was mitigated by embedding an interdigitated array of <100 $\mu$m wide channels in the electrodes using laser micromachining. The micron-scale dimensions of the resulting embedded, micro-interdigitated flow fields (e$\mu$-IDFFs) facilitate flow-through electrodes with high apparent permeability while minimizing active-material loss. Our modeling shows that these e$\mu$-IDFFs are more suitable for our intercalation electrodes because they have >100X lower permeability compared to common redox-flow battery electrodes, for which millimetric flow-channel widths were used exclusively in the past. Total desalination thermodynamic energy efficiency (TEE) was improved by more than ten-fold relative to unpatterned electrodes: 40.0% TEE for brackish water, 11.7% TEE for hypersaline brine, and 7.4% TEE for seawater-salinity feeds. Water transport between diluate and brine streams and charge efficiency losses resulting from (electro)chemical effects are implicated as limiting energy efficiency and water recovery, motivating their investigation for enhancing future FDI performance.Comment: 70 pages, 23 figures. Energy Environ. Sci. (2023

Electron-Electron Interactions in Artificial Graphene

Recent advances in the creation and modulation of graphene-like systems are introducing a science of "designer Dirac materials". In its original definition, artificial graphene is a man-made nanostructure that consists of identical potential wells (quantum dots) arranged in a adjustable honeycomb lattice in the two-dimensional electron gas. As our ability to control the quality of artificial graphene samples improves, so grows the need for an accurate theory of its electronic properties, including the effects of electron-electron interactions. Here we determine those effects on the band structure and on the emergence of Dirac points

A taxonomical framework of socio-cultural hazards in transport hubs

This article presents a taxonomical framework that supports the considerations of socio-cultural hazards that may affect crowd management in transport hubs, i.e. airports, ports, underground and train stations, both in normal and emergency situations. Such hazards include communication breakdowns with passengers due, for instance, to language barriers; increased potential for revolts, as in stranded passenger situations; misreporting of security threats; and uncooperative behaviour in case of emergencies. Such socio-cultural hazards are not normally considered from the integrated perspective of transport hub operators, e.g. security staff, first responders and service assistants as well as safety and security managers. The present study provides an integrated perspective of these hazards as a means to increase the performance of transport staff members that interact with the public and with passengers on a daily basis. The methodology used to develop the framework comprises: (i) a focus group with relevant experts, (ii) semi-structured interviews at operational facilities with front-end practitioners, and (iii) a review of academic literature and media reports. The framework has also been qualitatively corroborated with transport operators in dedicated interviews and a focus group session. The study identified 10 socio-cultural hazards that were combined into a single framework comprising three high-level sub-categories: (i) crowd–staff interactions, (ii) crowd–crowd interactions, and (iii) crowd–environment interactions. The framework of socio-cultural factors can increase staff’s awareness of relevant socio-cultural hazards, their potential consequences in both normal and emergency situations, and the associated mitigation strategies. In turn, this can increase the quality and continuity of service, safety and security in the management of members of the public and passengers in transport hubs

Modal Analysis and Coupling in Metal-Insulator-Metal Waveguides

This paper shows how to analyze plasmonic metal-insulator-metal waveguides using the full modal structure of these guides. The analysis applies to all frequencies, particularly including the near infrared and visible spectrum, and to a wide range of sizes, including nanometallic structures. We use the approach here specifically to analyze waveguide junctions. We show that the full modal structure of the metal-insulator-metal (MIM) waveguides--which consists of real and complex discrete eigenvalue spectra, as well as the continuous spectrum--forms a complete basis set. We provide the derivation of these modes using the techniques developed for Sturm-Liouville and generalized eigenvalue equations. We demonstrate the need to include all parts of the spectrum to have a complete set of basis vectors to describe scattering within MIM waveguides with the mode-matching technique. We numerically compare the mode-matching formulation with finite-difference frequency-domain analysis and find very good agreement between the two for modal scattering at symmetric MIM waveguide junctions. We touch upon the similarities between the underlying mathematical structure of the MIM waveguide and the PT symmetric quantum mechanical pseudo-Hermitian Hamiltonians. The rich set of modes that the MIM waveguide supports forms a canonical example against which other more complicated geometries can be compared. Our work here encompasses the microwave results, but extends also to waveguides with real metals even at infrared and optical frequencies.Comment: 17 pages, 13 figures, 2 tables, references expanded, typos fixed, figures slightly modifie

fMRI evidence of ‘mirror’ responses to geometric shapes

Mirror neurons may be a genetic adaptation for social interaction [1]. Alternatively, the associative hypothesis [2], [3] proposes that the development of mirror neurons is driven by sensorimotor learning, and that, given suitable experience, mirror neurons will respond to any stimulus. This hypothesis was tested using fMRI adaptation to index populations of cells with mirror properties. After sensorimotor training, where geometric shapes were paired with hand actions, BOLD response was measured while human participants experienced runs of events in which shape observation alternated with action execution or observation. Adaptation from shapes to action execution, and critically, observation, occurred in ventral premotor cortex (PMv) and inferior parietal lobule (IPL). Adaptation from shapes to execution indicates that neuronal populations responding to the shapes had motor properties, while adaptation to observation demonstrates that these populations had mirror properties. These results indicate that sensorimotor training induced populations of cells with mirror properties in PMv and IPL to respond to the observation of arbitrary shapes. They suggest that the mirror system has not been shaped by evolution to respond in a mirror fashion to biological actions; instead, its development is mediated by stimulus-general processes of learning within a system adapted for visuomotor control