The electronic states of cyclopropane studied by VUV absorption and ab initio multireference configuration interaction calculations

Abstract

The absolute photoabsorption cross-section of cyclopropane has been measured between threshold and 30 eV using monochromated synchrotron radiation. The spectrum is dominated by prominent broad peaks arising from electronic transitions into valence-excited states. Much weaker structure ascribed to Rydberg states associated with excitation from the 3e′ or 1a″2 orbitals is also discernible. Some of these Rydberg states display vibrational progressions which can be correlated with similar structure observed in the corresponding photoelectron spectrum. Ab initio multireference configuration interaction calculations have been performed to obtain excitation energies for valence electron transitions into Rydberg or virtual valence orbitals. These theoretical predictions have enabled assignments to be proposed for most of the observed absorption bands.