Optimal control within the density matrix formalism is applied to the production of desired non-equilibrium distributions in condensed phases. The time evolution of a molecular system modeled by a displaced harmonic oscillator is assumed to be described by the Markoffian master equation with phenomenological relaxation parameters. The physical objectives of concern are the creation of a specified vibronic state, population inversion and wave packet shaping. The effects of an initial thermal distribution and dissipation on these targets are examined. In order to transfer a large amount of population (i.e., the strong-field regime) to a target wave packet in an electronic excited state, it is shown that creating a shaped packet in the ground state is often required to achieve high yield. This control pathway cannot be taken into account within the weak-field approximation, and is especially important when the target state includes vibrational states that are weakly accessible from the initial state or that have preferential indirect excitation paths from the initial state. Although relaxation effects usually reduce the control efficiency, under certain conditions, the bath-induced dynamics can help to create an objective state.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry