Spectral characteristics of subcritical carbon dioxide in nanopores

Coherent anti-Stokes Raman scattering spectra measured within the Q-branch of the vibrational transition ν₁ are used to gain insights into the state of carbon dioxide molecules in nanopores of Vycor™ glass at room temperature (20.5°C) and a subcritical temperature of 30.5°C and gas pressures up to the saturation point P _sat for each temperature. Along with the main spectral component, belonging to gaseous CO₂ molecules, the spectra recorded at pressures close to P _sat feature a second (low-frequency) component. The second component is associated with the contribution from the CO₂ molecules trapped inside pores. A spectral deconvolution with account for the interference of these two bands makes it possible to estimate the spectral characteristics of the second (low-frequency) component at each temperature. At 20.5°C, the bandwidth of the low-frequency component decreases with CO₂ pressure, a behavior that can be explained by the transition of CO₂ from the adsorbed to the condensed state in the pore. At the subcritical temperature of 30.5°C, the spectral width of the second component is pressure-independent and close to the value measured in the bulk of the supercritical fluid, a result likely associated with a low-temperature shift of the critical point of the substance trapped in nanopores.     

Narrowing of the vibrational spectrum under compression of liquid carbon dioxide

The broadening and shift of the Q bands of the 1388/1285-cm⁻¹ Fermi doublet of carbon dioxide have been measured by means of the spectroscopy of coherent anti-Stokes Raman scattering in a wide density range realized at compression in dense gaseous and liquid states. The spectrum of the low-frequency Q band exhibits an essential narrowing upon the compression of the liquid in the density range of 320–400 amagat from a maximum width of about 2.2 cm⁻¹ to about 1.7 cm⁻¹ determined by elastic dephasing. The observed dependence is connected with the progressive narrowing of the spectral contribution attributed to the collapsed rotational structure.     

Mathematical Simulation of the Distribution of the Electron Beam Current during Pulsed Heating of a Metal Target

Journal of Applied and Industrial Mathematics - We study a model of the current distribution during heating of the surface of a tungsten sample under pulsed exposure to an electron beam. The model...     

Analytical model of brittle destruction based on hypothesis of scale similarity

The size distribution of dust particles in thermonuclear (fusion) devices is closely described by a power law, which may be related to the brittle destruction of materials. The hypothesis of scale similarity leads to the conclusion that the size distribution of particles formed as a result of a brittle destruction is described by a power law with the exponent ??? that can range from ?4 to ?1. The model of brittle destruction is described in terms of the fractal geometry, and the distribution exponent is expressed via the fractal dimension of packing. Under additional assumptions, it is possible to refine the ?? value and, vice versa, to determine the type of destruction using the measured size distribution of particles.     

CARS diagnostics of molecular media under nanoporous confinement

The CARS spectroscopy is used for the diagnostics of carbon dioxide in a nanoporous glass at temperatures ranging from room temperature (20.5°C) to the subcritical temperature (30.5°C) in the pressure range below the saturated-vapor pressure. The contributions of the gas-phase molecules, the molecular layer adsorbed from the gas phase on the pore surface, the condensed liquid-like phase, and the liquid interface in the vicinity of the pore surface can be selected using the analysis of the nonlinear spectral response. The spectral behavior of the carbon dioxide confined in nanopores at the subcritical temperature indicates a state that is similar to the supercritical fluid. This corresponds to a low-temperature shift of the critical point of the medium confined in nanopores.     

CARS diagnostics of fluid adsorption and condensation in small mesopores

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy is applied to diagnostics of phase behavior of a fluid in pores of nanoporous glasses. Samples with mean pore radii of 2 and 3.5 nm were filled with compressed carbon dioxide at near‐room temperatures. CARS spectra of the 1388 cm⁻¹ Q‐branch were measured at isothermal compressing in a wide pressure range including the transition from gaseous to condensed state. The spectra show specific transformations caused by fluid adsorption and condensation in nanopores. We have carried out calculations of the spectral profiles based on the phase behavior of carbon dioxide in cylindrical glass nanopores. Phase behavior modeling was performed using thermodynamic concepts of surface adsorption and capillary condensation. A good agreement between experimental spectra and calculations was obtained. The potential of CARS technique for the diagnostics of fluid phase behavior in pores and for the characterization of nanoporous host structure is discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Photo–induced processes in Ag and Eu β-diketonates incorporated into aerogel matrix of silicon dioxide by supercritical fluid impregnation

Samples of silicon dioxide aerogel with embedded Ag and Eu β-diketonate molecules are obtained by impregnation in supercritical carbon dioxide (SC-CO₂). The sample impregnated by Eu(tta)₃ molecules possesses photoluminescence properties. Moreover, adsorption of Eu(tta)₃ on the walls of the pores results in a strong broadening of the Stark components of its photoluminescence spectra. It is found that aerogel impregnation by AgFOD molecules followed by laser irradiation causes the formation of Ag nanoparticles in the sample volume as a result of AgFOD photolysis and subsequent diffusion self-assembly. The Ag nanoparticles assemble into filament structures due to self-organization as they focus laser radiation.     

Broadening of vibrational spectra of carbon dioxide upon absorption and condensation in nanopores

Coherent anti-Stokes Raman Spectroscopy (CARS) has been used to study the vibrational Q-branch with the frequency of 1388 cm^?1 of the ν₁ mode of carbon dioxide molecules filling a sample made of nanopore glass at room temperature (20.5°C). The measurements were carried out in a gas cell at pressures approaching saturation P _sat. When pressure was increased above 0.8 P _sat, in addition to the spectral component due to the gaseous phase molecules, the CARS spectra featured a component due to the molecules adsorbed on the pore walls. Simulation of spectra taking the interference of these two contributions into account enabled the estimation of the broadening of the vibrational molecular spectra in the adsorbed layer. The spectral width of the component due to the adsorbed molecules was nearly a factor of two times larger than that of molecules in the bulk liquid phase. At pressures above 0.94 P _sat, the spectral width of the component due to the adsorbed molecules decreased to values close to those measured in the bulk liquid phase, which corresponds to the condensation of molecules in nanopores.     

KLYPVE/TUS space experiments for study of ultrahigh-energy cosmic rays

The KLYPVE space experiment has been proposed to study the energy spectrum, composition, and arrival direction of ultrahigh-energy cosmic rays (UHECR) by detecting from satellites the atmosphere fluorescence and scattered Cherenkov light produced by EAS, initiated by UHECR particles. The TUS setup is a prototype KLYPVE instrument. The aim of the TUS experiment is to detect dozens of UHECR events in the energy region of the GZK cutoff, to measure the light background, to test the atmosphere control methods, and to study stability of the optical materials, PMTs, and other instrumental parts in space environment.