Vibrational lifetimes and vibrational line positions in polyatomic supercritical fluids near the critical point

Abstract

Picosecond infrared pump–probe experiments are used to measure the vibrational lifetime of the asymmetric (T1u) CO stretching mode of W(CO)6 in supercritical CO2, C2H6, and CHF3 as a function of solvent density and temperature. As the density is increased at constant temperature from low, gaslike densities, the lifetimes become shorter. However, in all three solvents, it is found that within a few degrees of the critical temperature (Tr≡T/Tc≈1.01), the lifetimes are essentially constant over a wide range of densities around the critical value (ρc). When the density is increased well past ρc, the lifetimes shorten further. At higher temperature (Tr=1.06) this region of constant vibrational lifetime is absent. Infrared absorption spectra of W(CO)6 and Rh(CO)2acac in supercritical CO2, C2H6, and CHF3 acquired for the same isotherms show that the vibrational spectral peak shifts follow similar trends with density. The peak positions shift to lower energy as the density is increased. Near the critical point, the peak positions are density independent, and then redshift further at densities well above ρc. It is shown that critical fluctuations play a dominant role in the observed effects. Theoretical calculations ascribe the density independence of the observables to the cancellation of various rapidly changing quantities near the critical point. The theory’s calculation of density independence implicitly involves averages over all local densities and does not involve any form of solute–solvent clustering.