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)4NO, Co(CO)3NO, Fe(CO)2(NO)2, Mn(NO)3CO and Cr(NO)4. The exchange-correlation potential is based on a combined functional of Beckeʹs exchange (B88) and Perdewʹs 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 Raimondiʹs rules for atomic screening. The average absolute deviation of the calculated core-electron binding energy from experiment is 0.28 eV.