LAUSR

Nonlinear-optical spectroscopic techniques that employ signals from the molecules located inside nanopores have promising potential for investigations of fluid behavior under nanoconfinement. Here, we apply coherent anti-Stokes spectroscopy to investigate the appearance of a liquid-like phase of carbon dioxide in mesoporous Vycor glass under isothermal compression. The spectra of the Q-branch (1388?cm?1) are registered at???11 ?C in a wide pressure range, starting from submonolayer coverage of the pore wall up to the bulk saturation pressure. Results show that a spectral contribution, similar to that of the bulk liquid, appears at relatively low pressure that is several times lower than the capillary-condensation pressure. The Raman shift of the peak is equal to that of the bulk liquid, although the linewidth is somewhat increased. The peak is attributed to the layers adsorbed beyond the monolayer or to small liquid-like clusters appearing in specific areas of the porous network. The spectroscopic approach presented here demonstrates the ability to detect and estimate small amounts of the liquid-like phase and to distinguish it from the layers strongly interacting with the pore surface.