Excitonic effects in two-dimensional vibrational spectra of liquid formamide

The linear and two-dimensional infrared (2DIR) responses of the amide I vibrational mode in liquid formamide are investigated experimentally and theoretically using molecular dynamics simulations. The recent method based on the numerical integration of the Schrödinger equation is employed to calculate the 2DIR spectra. Special attention is devoted to the interplay of the structural dynamics and the excitonic nature of the amide I modes in determining the optical response of the studied system. In particular, combining experimental data, simulated spectra and analysis of the simulated atomic trajectory in terms of a transition dipole coupling model, we provide a convincing explanation of the peculiar features of the 2DIR spectra, which show a substantial increase of the antidiagonal bandwidth with increasing frequency. We point out that, at variance with liquid water, the 2DIR spectral profile of formamide is determined more by the excitonic nature of the vibrational states than by the fast structural dynamics responsible for the frequency fluctuations

A Mid-Infrared Imaging Survey of Embedded Young Stellar Objects in the Rho Ophiuchi Cloud Core

Results of a comprehensive, new, ground-based mid-infrared imaging survey of the young stellar population of the Rho Ophiuchi cloud are presented. Data were acquired at the Palomar 5-m and at the Keck 10-m telescopes with the MIRLIN and LWS instruments, at 0.25 arcsec and 0.25 arcsec resolutions, respectively. Of 172 survey objects, 85 were detected. Among the 22 multiple systems observed, 15 were resolved and their individual component fluxes determined. A plot of the frequency distribution of the detected objects with SED spectral slope shows that YSOs spend ~400,000 yr in the Flat Spectrum phase, clearing out their remnant infall envelopes. Mid-infrared variability is found among a significant fraction of the surveyed objects, and is found to occur for all SED classes with optically thick disks. Large-amplitude near-infrared variability, also found for all SED classes with optically thick disks, seems to occur with somewhat higher frequency at the earlier evolutionary stages. Although a general trend of mid-infrared excess and NIR veiling exists proceeding through SED classes, with Class I objects generally exhibiting K-veilings > 1, Flat Spectrum objects with K-veilings > 0.58, and Class III objects with K-veilings =0, Class II objects exhibit the widest range of K-band veiling values, 0-4.5. However, the highly variable value of veiling that a single source can exhibit in any of the SED classes in which active disk accretion can take place is striking, and is direct observational evidence for highly time-variable accretion activity in disks. Finally, by comparing mid-infrared vs. near-infrared excesses in a subsample with well-determined effective temperatures and extinction values, disk clearing mechanisms are explored. The results are consistent with disk clearing proceeding from the inside-out.Comment: 18 pages + 5 tables + 7 figure

The Industrial Pattern of Italian Regions: A Disaggregated Sectoral Analysis Based on Input–Output Tables

Italy joined the so-called ‘Industry 4.0’ European framework in 2016, which designed and approved a national plan to regulate this key issue for regional development. To better support such a framework, the present study attempts to quantify the contribution of the Italian regions to the output formation process. More specifically, a multi-sectoral Input–Output (IO) model that supports national policies was proposed to cumulatively consider 29 industries that partition the Italian economy into representative branches at the level of administrative regions. Elementary input data were derived from the inter-sectoral table of the economy released by the Italian National Institute of Statistics (ISTAT). The economic outcomes of the Italian regions were estimated using a non-survey procedure, based on Flegg Location Quotients, to determine the upstream and downstream positions of each industry at country and regional levels. Indices grounded on the Hypothetical Extraction Method (HEM) further delineated the role each industry plays in the regional economy. The empirical findings of this study demonstrate how non-survey IO regionalization and the resulting industry-based indices provide appropriate knowledge for regional development policies

Economic Downturns, Urban Growth and Suburban Fertility in a Mediterranean Context

Despite the wealth of micro–macro data on short-term demographic dynamics, the impact of metropolitan growth and economic downturns on local fertility is still under-investigated in advanced economies. Recent studies in low-fertility contexts have assumed suburban birth rates as being systematically higher than urban and rural rates. This assumption (hereafter, known as the ‘suburban fertility hypothesis’) was grounded on stylized facts and spatial regularities that imply a significant role of both macro (contextual) and micro (behavioral) factors positively influencing fertility in suburban locations. To verify such a hypothesis from a macro (contextual) perspective, the present study compares the general fertility rate of urban, suburban, and rural settlements of the Athens’ metropolitan region (Greece) at various observation years between 1860 and 2020. Long-term Athens’ growth represented a sort of ‘quasi-experiment’ for Mediterranean Europe, linking sequential urban stages and distinctive waves of economic expansion and recession. Using multivariate exploratory analysis and global/local econometric models, a dominant ‘rural’ fertility regime was recorded for 1860 and 1884. A characteristic ‘urban’ fertility regime was, instead, found over a relatively long, intermediate period between 1956 and 1990. Higher fertility in suburban settlements (10 km away from downtown Athens, on average) was, finally, observed since 2000. Considering a sufficiently long-time interval, the existence of multiple fertility regimes along the distance gradient has demonstrated how fertility dynamics are intrinsically bonded with metropolitan growth, economic downturns, and social transformations in Mediterranean Europe

Indigo chromophores and pigments: structure and dynamics

In this study, we explore the molecular mechanisms of the stability of indigo chromophores and pigments. Assisted with density functional theory, we compare visible, infrared and Raman spectral properties of model molecules, chromophores and pigments derived from living organisms. Using indigo carmine as a representative model system, we characterize the structure and dynamics of the chromophore in the first electronic excited state using femtosecond visible pump-infrared probe spectroscopy. Results of experiments and theoretical studies indicate that, while the trans geometry is strongly dominant in the electronic ground state, upon photoexcitation, in the Franck-Condon region, some molecules may experience isomerization and proton transfer dynamics. If this happens, however, the normal modes of the trans geometry of the electronic excited state are reconfirmed within several hundred femtoseconds. Supported by quantum theory, first, we ascribe stabilization of the trans geometry in the Franck-Condon region to the reactive character of the potential energy surface for the indigo chromophore when under the cis geometry in the electronic excited state. Second, we suggest that a conical intersection crossing, due to the high barrier along the isomerization pathway in the ground state, would provide for the effective relaxation and observed dominance of the trans geometry of the chromophore in the ground state. Planarity of the chromophore under the trans geometry assists effective dissipation of energy via a cascade of in-plane C-C, C-O···H-N stretchings and C-C-C bending modes delocalized over the molecular mainframe. The described mechanisms help to explain the remarkable photo-stability of indigo chromophores

Mesure statistique de la résistance de contact d’une grille sérigraphiée pour cellules solaires au silicium multicristallin

La métallisation par sérigraphie est une des étapes les plus importantes dans la technologie d’élaboration des cellules solaires pour une production à grande échelle. Néanmoins, elle demeure dépendante de plusieurs paramètres variables. Pour le silicium multi cristallin, tout changement dans le procédé de réalisation des cellules solaires influence directement l’optimisation du profil de recuit de la métallisation par sérigraphie. Les plaquettes de silicium multi cristallin subissent toutes les étapes classiques de réalisation des cellules solaires comme le nettoyage chimique et la décontamination, une diffusion au phosphore et le dépôt du nitrure de silicium SiNx par PECVD (Plasma Enhanced Chemical Vapor Deposition). Il y a juste le dépôt du contact Argent Ag sur la face avant de la plaquette. Nous avons utilisé la pâte de sérigraphie Ag Ferro 3349. La grille métallique comporte six (06) motifs TLM (Transfer Length Method) pour les mesures de la résistance de contact. Le principal but de ce travail est le contrôle de la qualité du contact Ag/SiNx/n+-Si dans les cellules solaires au silicium multicristallin. Les mesures TLM révèlent une cartographie des valeurs de la résistance de contact pour chaque température. Le profil optimal de température de recuit est autour de 750 °C