Probing the Lowest-Lying Electronic States of Acrylic Acid by Experimental and Theoretical Methods

Abstract

We report a combined experimental and theoretical study of the electronic state spectroscopy of acrylic acid (CHO) in the gas phase, by high-resolution vacuum ultraviolet (VUV) photoabsorption measurements in the 4.0-10.8 eV energy range, together with ab initio calculations (vertical energies and oscillator strengths), which were used in the assignment of the valence transitions. We also discuss the Rydberg transitions for this molecular target, obtained using the experimental ionization energies available in the literature. The experimental spectrum presented in this paper represents the highest resolution data yet reported for acrylic acid and reveals new features not previously reported in the literature. The dominant transitions have been assigned to (π∗(4a″) → π (3a″)) and (π;∗(4a″) → π (2a″)), the latter exhibiting excitation of the ν5′(a′) C = O stretching mode with mean energy of 0.155 eV. The measured absolute photoabsorption cross sections have been used to calculate the photolysis lifetime of acrylic acid in the upper stratosphere (20-50 km).