Limonene: electronic state spectroscopy by high-resolution vacuum ultraviolet photoabsorption, electron scattering, He(i) photoelectron spectroscopy and ab initio calculations

Abstract

Electronic state spectroscopy of limonene has been investigated using vacuum ultraviolet photoabsorption spectroscopy in the energy range 5.0-10.8 eV. The availability of a high resolution photon beam (~0.075 nm) enabled detailed analysis of the vibrational progressions and allowed us to propose, for the first time, new assignments for several Rydberg series. Excited states located in the 7.5-8.4 eV region have been studied for the first time. A He(I) photoelectron spectrum has also been recorded from 8.2 to 9.5 eV and compared to previous low resolution works. A new value of 8.521 ± 0.002 eV for the ground ionic state adiabatic ionisation energy is proposed. Absolute photoabsorption cross sections were derived in the 10-26 eV range from electron scattering data. All spectra presented in this paper represent the highest resolution data yet reported for limonene. These experiments are complemented by new ab initio calculations performed for the three most abundant conformational isomers of limonene, which we then used in the assignment of the spectral bands.