Central atom 1s photoabsorption spectra of nitrogen and phosphorus AX 3 (A=N, P and X=F, H) molecules

Abstract

The newly commissioned SGM beamline [1] at CSRF (the Canadian Synchrotron Radiation Facility at the Synchrotron Radiation Center in Madison WI) offers excellent performance at the nitrogen 1s absorption edge. We have therefore expanded our ongoing X-ray absorption spectroscopy study of electronic structure and chemical bonding of small molecules to include measurements of the N(1s) absorption edges for comparison to the edges of heavier elements in the same group. Here we present the central atom (N, P) 1s spectra of NF 3, NH 3, PF 3 and PH 3 measured at high resolution with synchrotron radiation. The phosphorus edges were measured with the Canadian DCM beamline at CSRF. The observed features were assigned with the aid of MS-Xα and ab initio calculations. Spectral differences are explained in terms of differences in the electronic structure of these four related molecules. All molecules show a strong central atom (A) core (1s) to 1e * transition and additional weaker features which arise from transitions to other virtual molecular orbitals. Chemical shifts resulting from the molecular field of the substituents are observed. Our NH 3 spectrum agrees with that previously published [2].