Density functional calculation of core-electron binding energies of transition metal carbonyl and nitrosyl complexes

Our recent procedure of the unrestricted generalized transition state (uGTS) model for density functional calculations of core-electron binding energies has been applied to seven carbonyl and nitrosyl inorganic complexes: Fe(CO)(5), Ni(CO)(4), Mn(CO)(4)NO, Co(CO)(3)NO, Fe(CO)(2)(NO)(2), Mn(NO)(3)CO and Cr(NO)(4). The exchange-correlation potential is based on a combined functional of Becke’s exchange (B88) and Perdew’s correlation (P86). The cc-pVTZ basis set was used for the calculation of neutral molecules, while for the partial cation created in the uGTS approach we scaled the cc-pVTZ basis set using a procedure based on Clementi and Raimondi’s rules for atomic screening. The average absolute deviation of the calculated core-electron binding energy from experiment is 0.28 eV.