Design of an ultrashort optical transmission cell for vacuum ultraviolet spectroscopy of supercritical fluids.

We present the design and characteristics of an ultrathin flow cell optimized for vacuum ultraviolet transmission spectroscopy experiments on supercritical fluids. The cell operates satisfactorily at pressures up to 300 bar and temperatures up to 390 °C. The variable path length concept of the cell allows for optical transmission studies of analytes ranging from dense condensed-phase systems to gas-phase systems. The path length of the cell can be adjusted from hundreds of nanometers to hundreds of micrometers by an exchange of a variable thickness spacer sandwiched between two sapphire windows. In the path length range from nanometers to single micrometers, metal vapor deposited on one or both of the two sandwiched optical windows constitute the spacer. Spacers with thicknesses of 2 μm and greater can be constructed from simple commercially available metal foils. The cell has been used to measure the lowest-lying absorption band of water in both the vapor and condensed phases from room temperature up to and above the critical point. It has also found application in the studies of aqueous ions and nonaqueous liquids including various common organic solvents and carbon dioxide.