Theoretical study on the core-excited states of the allyl using CVS-icMRCISD method

Abstract

The allyl radical (C3H5) is a well-characterized hydrocarbon radical, renowned for its pivotal role as an intermediate species in high-energy environments. Its core excited states can elucidate intricate details pertaining to its electronic and structural properties. The core excited states of allyl were studied experimentally using X-ray absorption spectroscopy (XAS), and the primary characteristic peaks were assigned using the MCSCF approach, but not entirely. In this work, the recently developed CVS-icMRCISD scheme was used to simulate the excitation and ionization processes of C's K-shell electrons within allyl radicals, cations, and anions, respectively. Our results indicate that the XAS spectrum obtained not merely captured the distinctive peaks associated with allyl radicals, but also encompassed the characteristic peaks pertaining to allyl cations. Meanwhile, unlike manually adjusting the state weights of different electronic states to align with experimental spectral data, we adopt the CVS-icMRCISD scheme, which uses state averaging and produces unbiased results, making it suitable for studying multiple states simultaneously and easy to converge. More importantly, when accounting for the dynamic electron correlation, our results align seamlessly with the experimental XAS. This congruence underscores the potential of our CVS-icMRCISD as a robust tool for theoretical investigations pertaining to the excitation of inner shell electrons in small molecules.