Toward the laser control of electronic decoherence.

Abstract

Controlling electronic decoherence in molecules is an outstanding challenge in chemistry. Recent advances in the theory of electronic decoherence [B. Gu and I. Franco, J. Phys. Chem. Lett. 9, 773 (2018)] have demonstrated that it is possible to manipulate the rate of electronic coherence loss via control of the relative phase in the initial electronic superposition state. This control emerges when there are both relaxation and pure-dephasing channels for decoherence and applies to initially separable electron-nuclear states. In this paper, we demonstrate that (1) such an initial superposition state and the subsequent quantum control of electronic decoherence can be created via weak-field one-photon photoexcitation with few-cycle laser pulses of definite carrier envelope phase (CEP), provided the system is initially prepared in a separable electron-nuclear state. However, we also demonstrate that (2) when stationary molecular states (which are generally not separable) are considered, such one-photon laser control disappears. Remarkably, this happens even in situations in which the initially factorizable state is an excellent approximation to the stationary state with fidelity above 98.5%. The laser control that emerges for initially separable states is shown to arise because these states are superpositions of molecular eigenstates that open up CEP-controllable interference routes at the one-photon limit. Using these insights, we demonstrate that (3) the laser control of electronic decoherence from stationary states can be recovered by using a two-pulse control scheme, with the first pulse creating a vibronic superposition state and the second one inducing interference. This contribution advances a viable scheme for the laser control of electronic decoherence and exposes a surprising artifact that is introduced by widely used initially factorizable system-bath states in the field of open quantum systems.