Time-resolved optical probing of the non-equilibrium supercritical state in molecular media under ns laser-plasma impact.

We proposed a complex method based on a combination of shadow photography and time-resolved Raman spectroscopy to observe the non-stationary laser-induced supercritical state in molecular media. Shadow photography is applied for retrieving pressure values, while Raman spectroscopy with molecular dynamics for temperature estimation. Time resolution of 0.25 ns is achieved by varying the delay between the pump (creating an extreme energy delivery) and the probe laser pulses by the self-made digital delay electronic circuit . The proposed method was employed in liquid carbon dioxide and water. Under nanosecond laser pulse impact, the estimated temperatures and pressures (∼700 K and ∼0.5 GPa) achieved in media are higher than the critical parameters of the samples.

The Anomalous Behavior of Thermodynamic Parameters in the Three Widom Deltas of Carbon Dioxide-Ethanol Mixture.

Using molecular dynamics, we demonstrated that in the mixture of carbon dioxide and ethanol (25% molar fraction) there are three pronounced regions on the p-T diagram characterized by not only high-density fluctuations but also anomalous behavior of thermodynamic parameters. The regions are interpreted as Widom deltas. The regions were identified as a result of analyzing the dependences of density, density fluctuations, isobaric thermal conductivity, and clustering of a mixture of carbon dioxide and ethanol in a wide range of pressures and temperatures. Two of the regions correspond to the Widom delta for pure supercritical carbon dioxide and ethanol, while the third region is in the immediate vicinity of the critical point of the binary mixture. The origin of these Widom deltas is a result of the large mixed linear clusters formation.

Optical Diagnostics of Supercritical CO2 and CO2-Ethanol Mixture in the Widom Delta.

The supercritical CO2 (scCO2) is widely used as solvent and transport media in different technologies. The technological aspects of scCO2 fluid applications strongly depend on spatial-temporal fluctuations of its thermodynamic parameters. The region of these parameters' maximal fluctuations on the p-T (pressure-temperature) diagram is called Widom delta. It has significant practical and fundamental interest. We offer an approach that combines optical measurements and molecular dynamics simulation in a wide range of pressures and temperatures. We studied the microstructure of supercritical CO2 fluid and its binary mixture with ethanol in a wide range of temperatures and pressures using molecular dynamics (MD) simulation. MD is used to retrieve a set of optical characteristics such as Raman spectra, refractive indexes and molecular refraction and was verified by appropriate experimental measurements. We demonstrated that in the Widom delta the monotonic dependence of the optical properties on the CO2 density is violated. It is caused by the rapid increase of density fluctuations and medium-sized (20-30 molecules) cluster formation. We identified the correlation between cluster parameters and optical properties of the media; in particular, it is established that the clusters in the Widom delta acts as a seed for clustering in molecular jets. MD demonstrates that the cluster formation is stronger in the supercritical CO2-ethanol mixture, where the extended binary clusters are formed; that is, the nonlinear refractive index significantly increased. The influence of the supercritical state in the cell on the formation of supersonic cluster jets is studied using the Mie scattering technique.

3.5-mJ 150-fs Fe:ZnSe hybrid mid-IR femtosecond laser at 4.4 µm for driving extreme nonlinear optics.

We report on entering a new era of mid-IR femtosecond lasers based on amplification in a relatively new gain chalcogenide medium, Fe:ZnSe. Our hybrid all-solid-state laser system is based on direct pulse amplification of femtosecond seed from three-stage AGS-based-optical parametric amplification (OPA) in a Fe:ZnSe laser crystal optically pumped by a Cr:Yb:Ho:YSGG Q-switched nanosecond laser. The development of the pump source with output energy up to 90 mJ operating at a 10 Hz repetition rate regime and highly efficient grating compressor (80%) provides 3.5-mJ 150-fs femtosecond pulses centered at 4.4 µm. Diode-pumped Er:YAG/Er:YLF lasers make it possible to increase the beam quality and repetition rate of the proposed laser system up to 100 Hz. Focusing such a laser radiation into the ∼3λ beam diameter allows us to reach a focus laser intensity up to 1016 W/cm2 which is only an order of magnitude lower than a relativistic intensity of 1017 W/cm2 and enough to drive strong nonlinear optics in mid-IR. We show as a proof-of-principle experiment the generation of four-octave spanning (from 350 nm up to 5.5 µm) supercontinuum in xenon.

Anomalous behavior of nonlinear refractive indexes of CO2 and Xe in supercritical states.

Direct measurement of pressure dependent nonlinear refractive index of CO2 and Xe in subcritical and supercritical states are reported. In the vicinity of the ridge (or the Widom line), corresponding to the maximum density fluctuations, the nonlinear refractive index reaches a maximum value (up to 4.8*10-20m2/W in CO2 and 3.5*10-20m2/W in Xe). Anomalous behavior of the nonlinear refractive index in the vicinity of a ridge is caused by the cluster formation. That corresponds to the results of our theoretical assumption based on the modified Langevin theory.