Laser control in open quantum systems: preliminary analysis toward the Cope rearrangement control in methyl-cyclopentadienylcarboxylate dimer
Résumé
We present a preliminary simulation toward the control of the Cope rearrangement of the most stable isomer of methyl-cyclopentadienylcarboxylate dimer. An experimental investigation of the dimerization of methyl-cyclopentadienylcarboxylate has been carried out. It shows that the most stable isomer of the dimer, the Thiele's ester, is the major product of the dimerization. The simulation takes it as the initial state for the further control of the Cope reaction. The aim of the simulation is to examine the possibility of laser control to form the target product, not detected during the dimerization. The relevant stationary states have been characterized at the DFT B3LYP level, particularly the Cope transition state in which the dimer is connected only by a single bond r(1). A minimum energy potential surface has been computed in a two-dimensional subspace of two bounds r(2) and r(3) which achieve the dimerization and have a very high weight in the reaction path from the Cope TS to the two adducts. Quantum wave packet optimal control simulation has been studied in a one-dimensional model using an active coordinate r(-) - r(3) - r(2) which nearly corresponds to the reaction path. The stability of the optimal field against dissipation is examined by a non-Markovian master equation approach, which is perturbative in the system-bath coupling but without limitation on the strength of the field.