Optical Kerr effect of liquid and supercooled water: the experimental and data analysis perspective

The time-resolved optical Kerr effect spectroscopy (OKE) is a powerful experimental tool enabling accurate investigations of the dynamic phenomena in molecular liquids. We introduced innovative experimental and fitting procedures, that permit a safe deconvolution of sample response function from the instrumental function. This is a critical issue in order to measure the dynamics of sample presenting weak signal, e.g. liquid water. We report OKE data on water measuring intermolecular vibrations and the structural relaxation processes in an extended temperature range, inclusive of the supercooled states. The unpreceded data quality makes possible a solid comparison with few theoretical models; the multi-mode Brownian oscillator model, the Kubo's discrete random jump model and the schematic mode-coupling model. All these models produce reasonable good fits of the OKE data of stable liquid water, i.e. over the freezing point. The features of water dynamics in the OKE data becomes unambiguous only at lower temperatures, i.e. for water in the metastable supercooled phase. Hence this data enable a valid comparison between the model fits. We found that the schematic mode-coupling model provides the more rigorous and complete model for water dynamics, even if is intrinsic hydrodynamic approach hide the molecular information

Time resolved optical Kerr effect analysis of urea–water system

The nuclear dynamics of urea aqueous solution was analyzed by time resolved optical Kerr effect (OKE). The data analysis was achieved in time and in frequency domains. Three relaxation times characterize the time decay of the OKE signal at high mole fractions of urea, while only two relaxation times characterize this decay for the low mole fractions. The observed slowest relaxation time increases with increasing the mole fraction of urea. The comparison between this relaxation time and the ones determined by Raman and nuclear magnetic resonance spectroscopies suggests that the slow relaxation time is related to the reorientation of an axis lying in the plane of the urea molecule. At high mole fractions, the power spectra derived from the Fourier transform of the OKE signal are characterized by one broad peak at around 70 cm−1 and by a shoulder at around 160 cm−1 in the high frequency part of the former peak. This shoulder is related to the hydrogen bond interactions which involve urea molecules. Molecular dynamics simulation results on urea/water system suggest that the power spectra derived from OKE data could be interpreted in terms of translational motions (caging effect) and in terms of rotational motion (libration) of urea molecules

Acoustic complexity indices reveal the acoustic communities of the old-growth Mediterranean forest of Sasso Fratino Integral Natural Reserve (Central Italy)

The Sasso Fratino Integral Natural Reserve (Central Italy), a rare example of climax Mediterranean forest, provides an extraordinary opportunity to create an important soundscape reference of old-growth forest. In this study, we describe the soundscape of three localities (Lama, Sasso 950, Sasso 1400) representative of a gradient of variety and complexity of habitats, recorded during the period 10 May to 9 June 2017. Our results reveal temporal partitioning into acoustically homogeneous periods across 24 h suggesting that soniferous species (mainly birds) adopt ecological routines in which their acoustic activity is organized according to specific transient physiological needs. We processed multi-temporal aggregates of 1, 5, 10, and 15 s recordings and calculated the Acoustic Signature (AS) with four new indices: Ecoacoustic Events (EE), Acoustic Signature Dissimilarity (ASD), and their fractal dimensions (DEE and DASD), derived from the Acoustic Complexity Index (ACI). The use of the EE and ASD greatly improved the AS interpretation, adding further details such as the emergence of a clear sequence of patterns consistent with the daily evolution of the overall soundscape. DEE and DASD confirm the patterns observed using the AS, but provide more clarity and detail about the great acoustic complexity that exists across temporal scales in this old-growth forest. The temporal turnover of different acoustic communities occurs as a result of a gradual shift of different homogenous acoustic properties. We conclude that soniferous species use distinct, species-specific temporal resolutions according to their physiological and ecological needs and that the fractal approach used here provides a novel tool to overcome the difficulties associated with describing multi-temporal acoustic patterns

Labeled 15NO Study on N2 and N2O Formation Over Pt–Ba/Al2O3 NSR Catalysts

Mechanistic aspects involved in the formation of N2 and of N2O during the reduction of NO, stored nitrites and stored nitrates in the presence of NO are investigated in this work by means of isotopic labeling experiments over a model PtBa/Al2O3 NSR catalyst. The reduction of gaseous labeled NO with unlabelled NH3 leads to the formation of N2O at low temperature (below 180 °C), and of N2 at high temperature. All N2 possible isotopes are observed, whereas only labeled molecules have been detected in the case of N2O. Hence the formation of nitrous oxide involves undissociated NO molecules, whereas that of N2 can be explained on the basis of the statistical coupling of 15N- and 14N-adatoms on Pt. However, due to a slight excess of the mixed 15N14N isotope, a SCR-like pathway likely operates as well. The reduction of the stored labelled nitrates is very selective to N2 and all isotopes are observed, confirming the occurrence of the recombination pathway. However also in this case a SCR-like pathway likely occurs and this explains the abundance of the 14N15N species. When the reduction of the stored nitrates is carried out in the presence of NO, this species is preferentially reduced pointing out the higher reactivity of gaseous NO if compared to the nitrates

Relaxation of Vibrational Excitons in Molecular-Ionic Crystal s Measured by Picosecond Time-Resolved CARS

The decay times of the internal vibrations in K2S04, KCl04, NaN03 and CaC03 single crystals have been measured at different temperature s by picosecond time-resolved CARS. The low temperature experimental data and their temperature dependence are interpreted on the basis of an energy relaxation mechanism, involving two-phonon and higher order decay processes