Acetone photophysics at 282 nm excitation at elevated pressure and temperature. I: absorption and fluorescence experiments

Abstract

This is the first in a series of two papers that presents new experimental data to extend the range of acetone photophysics to elevated pressure and temperature conditions. In this work, a flexible static and flow system is designed and characterized to study the independent as well as coupled effect of elevated pressure and temperature on acetone photophysics over pressures of 0.05‒4.0 MPa and temperatures of 295‒750 K for 282 nm excitation wavelength in nitrogen and air as bath gases. Experimental results show that at 282 nm excitation, relative fluorescence quantum yield increases with increasing pressure, decreases with increasing temperature, and that the pressure sensitivity varies weakly with elevated temperature. The previously assumed linearity of fluorescence with tracer number density is shown to only be valid over a small range. Additionally, acetone fluorescence is only moderately quenched in the presence of oxygen. The present findings yield insight into the competition between the non-radiative and collisional rates at elevated temperature and pressure, as well as provide validation datasets for an updated fluorescence model developed in the second paper.