Photochemistry of organometallics: potential energy surfaces and reaction mechanisms

Abstract- Configuration interaction calculations, based on Complete Active Space SCF wavefunctions, are reported for the lowest excited states of Fe(COI,, HMn(CO), and HCo(CO),. Potential energy curves have been computed at the same level of accuracy for the photodissociation of HCo(CO),. The mechanism of the photochemical reactions of these organometallics is discussed. The cis stereospecificity of photosubstitution of d6 metal carbonyls is explained on the basis of state correlation diagrams. th