An ab initio study of Fe(CO)n, n=1,5, and Cr(CO)6

Abstract

Ab initio calculations have been performed for Cr(CO)6 and Fe(CO)n, n=1,5. Basis sets of better than double zeta quality are used and correlation is included using the modified coupled-pair functional method. The computed geometries and force constants are in reasonable agreement with experiment The sequential bond dissociation energies of CO from Fe(CO) 5 are estimated to be: 39, 31, 25, 22, and >5 kcal/mol. We note that the first bond dissociation energy is relative to the singlet ground state of Fe(CO)5 and the lowest singlet state of Fe(CO)4, whereas the second is relative to the ground triplet states of Fe(CO) 4 and Fe(CO)3. In addition, the binding energy for Fe-CO would be modified to 18 kcal/mol if dissociation occurred to the Fe( 5F) excited state asymptote. The CO binding energies for Fe and Cr are found to be in poorer agreement with experiment than those found in a previous study on Ni(CO)4. The origins of this difference are discussed. © 1991 American Institute of Physics.