Near-edge core photoabsorption in polyenes

Abstract

We present calculations on near-edge x-ray absorption fine structures (NEXAFS) in polyenes based on a newly derived direct, atomic orbital, static exchange method. The trends of different NEXAFS features with respect to the site of ionization and with respect to the number of ethylene subunits in the oligomer chain are studied. The trends for energies and intensities are found to be regular and alternant. A substantial reduction of the π to σ intensity ratios with the number of ethylene subunits is predicted, indicating delocalization of the screening π electrons. In contrast to NEXAFS spectra of a heterogeneous group attached to hydrocarbon chains, the NEXAFS spectra of oligomer sequences, here the polyenes, converge slowly. The building block principle is less appropriate than the final state rule for rationalizing the present findings.