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THz time domain spectroscopy is a powerful technique enabling the investigation of different materials in the far-infrared frequency range. Even if nowadays this technique is well established, its application to very thin films remains particularly difficult. We investigated the utilization of THz spectroscopy on samples of micrometric thickness with the aim to disentangle multiple reflections and to measure with high accuracy the absolute values of the material parameters. We implemented an experimental and data analysis procedure that can be applied to free-standing single-layers or multi-layers samples. Specifically, we report on the experimental investigation by THz time domain spectroscopy of two samples: a test sample made of two layers of known thickness and materials; and a second sample, that is of a great interest for cultural heritage studies, made of a thin film of ink layered on a thicker support. Moreover, we describe in details the data analysis and fitting procedures needed to extract the material parameters from the experimental results., Comment: arXiv admin note: text overlap with arXiv:1610.01025

THz time-domain spectroscopy in transmission mode was applied to study dry and wet drawing inks. In specific, cochineal-, indigo- and iron-gall based inks have been investigated; some prepared following ancient recipes and others by using synthetic materials. The THz investigations have been realized on both pellet samples, made by dried inks blended with polyethylene powder, and layered inks, made by liquid deposition on polyethylene pellicles. We implemented an improved THz spectroscopic technique that enabled the measurement of the material optical parameters and thicknesses of the layered ink samples on absolute scale. This experimental investigation shows that the THz techniques have the potentiality to recognize drawing inks by their spectroscopic features.

Dry and wet drawing materials were investigated by THz time-domain spectroscopy in transmission mode. Carbon-based and iron-gall inks have been studied, some prepared following ancient recipes and others using current synthetic materials; a commercial ink was studied as well. We measured the THz signals on thin film of liquid inks deposited on polyethylene pellicles, comparing the results with the thick pellets of dried inks blended with polyethylene powder. This study required the implementation of a new experimental method and data analysis procedure able to provide a reliable extraction of the material transmission parameters from a structured sample composed of thin layers, down to thickness of few tens of micrometers. THz measurements on thin ink layers enabled the determination of both the absorption and the refractive index in an absolute scale in the 0.1 - 3 THz range, as well as the layer thickness. THz spectroscopic features of a paper sheet dyed by one of the iron-gall inks were also investigated. Our results showed that THz time-domain spectroscopy enables to discriminate the various inks on different supports, including the application on paper, together with a proper determination of the absorption coefficients and indices of refraction.

We investigated the vibrational dynamics and the structural relaxation of water nanoconfined in porous silica samples with pore size of 4 nm at different levels of hydration and temperature. We used as spectroscopic technique the time-resolved optical Kerr effect, which enables to investigate the ultrafast water dynamics in a wide time (0.1-10 picosecond) or frequency (10-0.1 THz) window. At low levels of hydration, corresponding to two complete superficial water layers, no freezing occurs and the water remains mobile at all the investigated temperatures, while at the fully hydration we witness to a partial ice formation at about 248 K that coexists with the part of surface water remaining in the supercooled state. At low hydration, both structural and vibrational dynamics show significant modifications compared to the bulk liquid water due to the strong interaction of the water molecules with silica surfaces. Inner water, instead, reveals relaxation dynamics very similar to the bulk one., Comment: 10 pages 9 figures

Using heterodyne-detected optical Kerr effect (HD-OKE) measurements, we investigate the vibrational dynamics and the structural relaxation of water nanoconfined in Vycor porous silica samples (pore size $\simeq~4~nm$ ) at different levels of hydration and temperatures. At low level of hydration, corresponding to two complete superficial water layers, no freezing occurs and water remains mobile at all the investigated temperatures with dynamic features similar, but not equal, to the bulk water. The fully hydrated sample shows formation of ice at about 248 K, this process does not involve all the contained water; a part of it remains in a supercooled phase. The structural relaxation times measured from the decay of the time-dependent HD-OKE signal shows temperature dependence largely affected by the hydration level; the low frequency ($\nu<500~cm^{-1}$) vibrational spectra, obtained by the Fourier transforms of HD-OKE signal, appears less affected by confinement., Comment: submitted to Journal of Physics: Condensed Matter. arXiv admin note: text overlap with arXiv:1304.7989

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.

The low frequency vibrational spectra of hydrated porous silica are specifically sensitive to the hydrogen bond interactions and provides a wealth of information on the structural and dynamical properties of the water contained in the pores of the matrix. We investigate systematically this spectral region of Vycor porous silica (pore size about 4 nm) for a series of samples at different levels of hydration, from the dry matrix to completely filled pores. The spectra are obtained as the Fourier transforms of time-resolved heterodyne detected optical Kerr effect (HD- OKE) measurements. The comparison of these spectra with that of bulk water allows us to extract and analyze separately the spectral contributions of the first and second hydration layers, as well as that of bulk-like inner water. We conclude that the extra water entering the pores above 10 % water/silica weight ratio behaves very similarly to bulk water. At lower levels of hydration, corresponding to two complete superficial water layers or less, the H-bond bending and stretching bands, characteristic of the tetrahedral coordination of water in the bulk phase, progressively disappear: clearly in these conditions the H-bond connectivity is very different from that of liquid water. A similar behavior is observed for the structural relaxation times, measured from the decay of the time-dependent HD-OKE signal. The value for the inner water is very similar to that of the bulk liquid; that of the first two water layers is definitely longer by about a factor 4. These findings should be carefully taken into account when employing pore confinement to extend towards lower temperatures the accessible temperature range of supercooled water.

The liquid and supercooled states of water show a series of anomalies whose nature is debated. A key role is attributed to the formation of structural aggregates induced by critical phenomena occurring deep in the supercooled region; the nature of the water anomalies and of the hidden critical processes remains elusive. Here we report a time-resolved optical Kerr effect investigation of the vibrational dynamics and relaxation processes in supercooled bulk water. The experiment measures the water intermolecular vibrations and the structural relaxation process in an extended temperature range, and with unprecedented data quality. A mode-coupling analysis of the experimental data enables to characterize the intermolecular vibrational modes and their interplay with the structural relaxation process. The results bring evidence of the coexistence of two local configurations, which are interpreted as high-density and low-density water forms, with an increasing weight of the latter at low temperatures.

We present a study of surface acoustic waves (SAW) propagation on a 1D phononic surface (PS) by mean of an heterodyne-detected transient reflecting grating experiment. We excited and detected coherent stationary SAWs characterized by variable wave-vectors. The measured SAW frequencies enables the characterization of the band diagram of this PS sample beyond the first Brillouin zone (BZ). Four different SAW frequencies have been revealed, whose band diagram show articulated dispersion phenomena. In order to address the nature of the investigated SAWs, the experimental results are compared with a numerical simulation of elastic modes based on a finite element model. The observed SAWs are addressed to four Bloch waves characterized by different frequencies and surface energy localization. Moreover, we measured the SAW propagation on a flat non-phononic part of the sample surface and compared it with results from the PS., Comment: 21 pages, 10 figures

We present heterodyne detected transient grating (HD-TG) measurements on 1D surface corrugated Phononic Crystal (PC) with characteristic band edge wave vector of $\pi/5$ $\mu$m$^{-1}$. This experimental investigation enables both the direct band diagram characterization of surface waves and a direct measurement of the group velocity dispersion. The experimental data are compared to the simulations performed with the structural-mechanic module of a finite element method software. In this work we show the presence of two band gaps, observe distinct types of surface waves and, for the first time to our knowledge, measure extremely slow waves in correspondence of the band edge wave vector., Comment: This paper has been withdrawn by the authors. A new version of this paper as been submitted as 1105.5982, so please go the this paper

We present heterodyne detected transient grating measurements on water filled Vycor 7930 in the range of temperature 20 - 90 degrees C. This experimental investigation enables to measure the acoustic propagation, the average density variation due the liquid flow and the thermal diffusion in this water filled nano-porous material. The data have been analyzed with the model of Pecker and Deresiewicz which is an extension of Biot model to account for the thermal effects. In the whole temperature range the data are qualitatively described by this hydrodynamic model that enables a meaningful insight of the different dynamic phenomena. The data analysis proves that the signal in the intermediate and long time-scale can be mainly addressed to the water dynamics inside the pores. We proved the existence of a peculiar interplay between the mass and the heat transport that produces a flow and back-flow process inside the nano-pores. During this process the solid and liquid dynamics have opposite phase as predicted by the Biot theory for the slow diffusive wave. Nevertheless, our experimental results confirm that transport of elastic energy (i.e. acoustic propagation), heat (i.e. thermal diffusion) and mass (i.e. liquid flow) in a liquid filled porous glass can be described according to hydrodynamic laws in spite of nanometric dimension of the pores. The data fitting, based on the hydrodynamic model, enables the extraction of several parameters of the water-Vycor system, even if some discrepancies appear when they are compared with values reported in the literature., Comment: 32 pages, 11 figures

The density response of supercooled glycerol to an impulsive stimulated thermal grating (q=0.63 micron^-1) has been studied in the temperature range (T=200-340 K) where the structure rearrangement (alpha-relaxation) and thermal diffusion occur on the same time scale. A strong interaction between the two modes occurs giving rise to a dip in the T-dependence of the apparent thermal conductivity and a flattening of the apparent alpha-relaxation time upon cooling. A non-equilibrium thermodynamic (NET) model for the long time response of relaxing fluids has been developed. The model is capable to reproduce the experimental data and to explain the observed phenomenology., Comment: to be published in PRE Rapid Commun

The dynamics of the fragile glass-forming o-ter-phenyl is investigated by time-resolved transient grating experiment with an heterodyne detection technique in a wide temperature range. We investigated the dynamics processes of this glass-former over more then 6 decades in time with an excellent signal/noise. Acoustic, structural and thermal relaxations have been clearly identify and measured in a time-frequency window not covered by previous spectroscopic investigations. A detailed comparison with the density response function, calculated on the basis of generalized hydrodynamics model, has been worked out.

The results of a Transient Grating experiment in a supercooled molecular liquid of anisotropic molecules and its theoretical interpretation are presented. These results show the existence of two distinct dynamical contributions in the response function of this experiment, density and orientation dynamics. These dynamics can be experimentally disentangled by varying the polarisation of the probe and diffracted beams and they have been identified and measured in a Heterodyne Detected experiment performed on m-toluidine. The results of the theory show a good qualitative agreement with the measurements at all temperatures., Comment: PDF format, 14 pages including 4 figures, accepted for publication in EPL. minor modifications