THE ELECTRON-AFFINITIES OF PF AND PF2

Theoretical investigations of the adiabatic electron affinities of PF and PF2 have been carried out. Large basis sets were used in this rese arch, ranging from TZ2Pf+diff up to aug-cc-pVQZ. The theoretical metho ds applied here were Hartree-Fock self-consistent-held (SCF) theory, s ingle and double excitation configuration interaction (CISD), single a nd double excitation coupled cluster (CCSD), and the CCSD(T) method, w hich adds perturbatively the connected triple excitations to the CCSD method. The results of this investigation show that three theoretical methods, DZP++ BHLYP, G2, and aug-cc-pVQZ CCSD(T) provide excellent ag reement with each other for the adiabatic electron affinities of PF an d PF2. The high level of theory used in this research suggests that th e adiabatic electron affinity of PF is about 0.75 eV, and that of PF2 is about 0.76 eV. These predictions are in contrast to the experimenta l values of 3.4 eV (for PF) and 1.4-1.6 eV (for PF2). (C) 1998 America n Institute of Physics. [S0021-9606(98)01703-6].