R. Eramo

Evidence of two distinct local structures of water from ambient to supercooled conditions

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.

Accuracy of remote sensing of water temperature by Raman spectroscopy.

We present an experimental study of the Raman spectrum of pure and synthetic seawater with respect to its salinity and temperature dependence. Experiments made in the laboratory with both cw and pulsed excitation yield information on the limits and applicability of the technique in actual experiments in the field. We have also performed an experimental analysis to determine the presence of stimulated Raman scattering and its influence on the temperature dependence of the spectrum.

Third-harmonic generation in positively dispersive gases with a novel cell

The generation of UV third-harmonic radiation by a focused laser beam in a positively dispersive gaseous medium is investigated. The nonlinear gas is confined to a focal half-space by using a differentially pumped gas cell. The resulting density gradient along the beam axis is shown to provide an efficient frequency conversion in spectral regions of positive dispersion. Experimental results obtained in argon at λ ~ 197 nm, which compare favorably with theory, are presented.

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 enable a safe deconvolution of sample response function from the instrumental function. This is a critical issue in order to measure the dynamics of 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 Kubos 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. We found that the schematic mode-coupling model provides the more rigorous and complete model for water dynamics, even if its intrinsic hydrodynamic approach does not give a direct access to the molecular information.

Laser-induced structure in the continuum of sodium: a weak dressing field measurement

We report an experimental study of a laser-induced resonance in the continuum of sodium, performed by measuring the modified atomic susceptibility. The sensitivity of the set-up has allowed the observation of the induced structure in conditions of relatively weak intensity of the dressing laser field, where the line shape is independent of the field amplitude and the comparison with theory is strict and direct. We have found a good agreement with theoretical predictions and measured the Fano parameter of the resonance.

A real-time acquisition system for pump–probe spectroscopy

An innovative acquisition system for time-resolved spectroscopy is presented. It is based on the real-time acquisition of the experimental signal during the rapid scan of an optical delay line and enables data acquisition with high absolute time resolution (1 femtosecond), high scanning velocity (2.5 cm/s) and long time delay (several nanoseconds). We report precise interferometric tests of the acquisition system, focusing on technical features of the optical delay line. We check this data acquisition technique by performing ultra-fast time-resolved experiments with laser sources of high and low repetition rates.

A spectrometer for high-resolution and high-contrast Brillouin spectroscopy in the ultraviolet

We present a multiple-grating spectrometer designed for high-resolution and high-contrast low-frequency scattering spectroscopy in the ultraviolet, as well as in the visible spectral regions. The instrument has a resolution better than 1 GHz and a contrast of about 1×10−10 both in the visible and in the UV range, thus doubling the highest resolution achieved by double-monochromator double-pass spectrometers such as the SOPRA DMDP2000, conceived for Raman–Brillouin spectroscopy using visible excitation. Performance tests and the Brillouin spectra obtained in the ultraviolet range are reported. Ray tracing results, aiming to give a better insight on the instrument performances are also presented. The instrument opens the possibility to study a new region of the exchanged momentum with a suitable energy resolution and to investigate the spectrum of density fluctuations in materials where the UV penetration depth could be a relevant step for the experimental study of the dynamics of disordered material.

Observation of a laser-induced structure in the ionization continuum of sodium atoms using photoelectron energy spectroscopy

We report an experimental analysis of a structure induced by a Nd:YAG laser embedding the sodium excited state in the ionization continuum. The induced structure is probed from the ground state via a one-photon ionization. The experiment is performed on an atomic beam apparatus which uses a time-of-flight spectrometer for energy analysing the emitted photoelectrons. The selectivity of this technique provides the best measurement of a laser-induced resonance in the photoionization spectrum reported to date. A good agreement is found between the theory and experimental results.

Ramsey spectroscopy of bound atomic states with extreme-ultraviolet laser harmonics

We report the experimental measurement of Ramsey interference fringes in the single-photon excitation to a high-lying bound state of atomic argon by pairs of phase-locked, time-delayed, extreme UV high-order-harmonic pulses at 87 nm. High-visibility Ramsey fringes are observed for delays larger than 100 ps, thus demonstrating a potential resolving power >10(5) at this wavelength.

Multiphoton time-delay spectroscopy using not transform-limited laser pulses

We report on a two-photon resonant three-photon ionisation experiment performed on atomic barium with a sequence of two identical not transform-limited laser pulses in the weak field regime. We show that our results, obtained by a multimode nanosecond laser source, can be reproduced theoretically by using much shorter transform-limited pulses with the same spectral bandwidth.