Ultrafast non-adiabatic laser-induced photodissociation dynamics of CpMn(CO)3. An ab initio quantum chemical and dynamical study

Abstract

The ultrafast laser driven dynamics of CpMn(CO)₃, so-called cymantrene, have been investigated by wavepacket propagations on adiabatic coupled CASSCF/MR-CCI potential energy curves calculated for the electronic ground and low-lying metal-centered (MC) excited ¹A′ and ¹A″ states as a function of one Mn–CO bond elongation. The main features of the absorption spectrum as well as the electronic states populations are investigated by the time-dependent approach including numerical non-adiabatic couplings. The photo-induced simulations use selected laser pulse parameters close to the experimental ones (Daniel et al., Chem. Phys., 2001, 267, 247), where the frequencies correspond to the four main resonant Franck-Condon transitions which can prepare either the parent neutral molecule [CpMn(CO)₃]* or the first photofragment [CpMn(CO)₂]*.