Electron affinities of heavier phosphoryl and thiophosphoryl halides APX3 (A = O, S and X = Br, I)

We carried out computational studies of OPX₃ and SPX₃ (X = Br and I) molecules and their corresponding anions using density functional theory, Møller‐Plesset, and CCSD(T) methods with newly developed model core potentials (MCP). Reliabilities of the MCP were demonstrated by comparing experimental and calculated results. We computed the geometric structure, electron affinities, and electrostatic moments using systematic sequences of the dzp‐, tzp‐, and qzp‐quality basis sets. Both C_3v and C_s symmetries were assumed to ascertain that minima on the potential energy surface were found. Infrared and Raman frequencies were calculated and compared with available experimental data. Natural population analyses were performed and used to determine distribution of the extra electron in anions. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007