Control by decoherence: weak field control of an excited state objective

Physics

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Scientific paper

Coherent control employing a broadband excitation is applied to a branching reaction in the excited state. In a weak field for an isolated molecule, a control objective is only frequency dependent. This means that phase control of the pulse cannot improve the objective beyond the best frequency selection. Once the molecule is put into a dissipative environment a new timescale emerges. In this study, we demonstrate that the dissipation allows us to achieve coherent control of branching ratios in the excited state. The model studied contains a nuclear coordinate and three electronic states: the ground and two coupled diabatic excited states. The influence of the environment is modeled by the stochastic surrogate Hamiltonian. The excitation is generated by a Gaussian pulse where the phase control introduced a chirp to the pulse. For sufficient relaxation, we find significant control in the weak field depending on the chirp rate. The observed control is rationalized by a timing argument caused by a focused wavepacket. The initial non-adiabatic crossing is enhanced by the chirp. This is followed by energy relaxation which stabilizes the state by having an energy lower than the crossing point.

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