High-resolution gas phase P L-edge photoabsorption spectra of PF5

Abstract

High-resolution photoabsorption spectra of P 2s and 2p levels of PF5 are reported. Fine structure, due to spin-orbit and ligand field splittings together with strong vibrational progression, is resolved in the Rydberg region of the P 2p spectrum. A ligand field splitting of 31 meV for the 2p3/2 orbital is obtained from the fit of the Rydberg transitions. The Franck–Condon fit analysis revealed that the vibrational progression of the higher Rydberg states is different from that of the valence-Rydberg mixed 4s state. In particular, we derived a decrease in P–F bond distances of 12 and 28 pm for the 4s valence-Rydberg mixed state and the high nl Rydberg states, respectively. The natural linewidths of the P 2p levels were determined to be 55 meV.Key words: PF5, Rydberg state, vibrational, ligand field splitting, photoabsorption.