Valence band photoemission and near-edge core excitation spectroscopy of di-t-butylchlorophosphine

The electronic structure of di-t-butylchlorophosphine [(t-butyl)2PCl] has been studied by photoemission spectroscopy (PES) and inner-shell electronic spectroscopy. The photoemission spectrum of (t-butyl)2PCl exhibits features in good agreement with molecular orbital assignments based on modified neglect of differential overlap semiempirical calculations. The unoccupied electronic structure of (t-butyl)2PCl has been investigated through P2p, P2s, Cl2p, and C1s core excitation spectra recorded by dipole-regime inner shell electron energy loss spectroscopy (ISEELS). The P2p and P2s spectra of (t-butyl)2PCl exhibit features in common with PCl3 and P(CH3)3, whereas the Cl2p spectrum resembles that of PCl3 and the C1s spectrum resembles P(CH3)3. Comparison of the photoemission and the ISEELS results emphasizes the local structural sensitivity of core excitation in contrast to the more extended picture of electronic structure provided by PES.