Quantum optimal control mechanisms are investigated for the selective metal-ligand dissociation of two organometallic
molecules: tetracarbonylmethylcobalt CH3Co(CO)4 and tricarbonylcyclopentadienylmanganese
A comparative study of the electronic structure of RCo(CO)4 (R= CH3, H) complexes
at the equilibrium and asymptotic geometry, which describes the dissociation of the axial ligands, is made. From this study,
the five lowest-lying electronic states, corresponding to the ground state, two metal-to-sigma-bond charge transfer (MSBCT)
states, and two metal-to-ligand charge transfer (MLCT) states are correlated, and the two-dimensional potential energy surfaces
for these states are calculated. Quantum dynamic simulations for both complexes are performed. The autocorrelation function is
recorded for both systems and is Fourier transformed to obtain theoretical absorption spectra which are discussed. The quantum
dynamics occurring on the unbound MSBCT states for the hydrido complex indicate a pure dissociation of the hydrogen ligand
whereas the dynamics for the methyl cobalt complex indicate a simultaneous breakage of both axial ligands. A pump-dump type of
control mechanism is employed to investigate the possible single CO or CH3 ligand dissociation from the CH3 Co(CO)3
complex. Selective single Co-CH3 bond dissociation is achieved.
The theory of nonresonant multiphoton transitions
(NMT) in the field of femtosecond spectroscopy is presented in a nonperturbative approach. The outcome of this approach is an
effective time-dependent Schrödinger equation. Furthermore, the theory of NMT is implemented for the first time into standard
optimal control theory (OCT). The organometallic molecule, CpMn(CO)3, is used as the model system for subsequent
control experiments. The extention of NMT to OCT is exemplified using an electronic two-level system of CpMn(CO)3.
Several control tasks are achieved via nonresonant two- and three-photon transitions.