A molecular system in contact with a bath undergoes strong decoherence processes. We examine a control scheme to minimize dissipation, while maximally retaining coherent evolution, by relating the evolution of the molecule to that of an identical freely propagating system. We seek a driving field that maximizes the projection of the open molecular system onto the freely propagated one. The evolution in time of a molecular system consisting of two nonadiabatically coupled electronic states interacting with a bath is followed. The driving control field that overcomes the decoherence is calculated. A proposition to implement the scheme in the laboratory using feedback control is suggested.
A molecular system in contact with a bath undergoes strong decoherence processes. We examine a control scheme to minimize dissipation, while maximally retaining coherent evolution, by relating the evolution of the molecule to that of an identical freely propagating system. We seek a driving field that maximizes the projection of the open molecular system onto the freely propagated one. The evolution in time of a molecular system consisting of two nonadiabatically coupled electronic states interacting with a bath is followed. The driving control field that overcomes the decoherence is calculated. A proposition to implement the scheme in the laboratory using feedback control is suggested.
Enviroment - caused dissipation disrupts the hamiltonian evolution of all quantum systems not fully isolated from any bath. We propose and examine a feedback-control scheme to eliminate such dissipation, by tracking the free hamiltonian evolution. We determine a driving-field that maximizes the projection of the actual molecular system onto the freely propagated one. The evolution of a model two level system in a dephasing bath is followed, and the driving field that overcomes the decoherence is calculated. An implementation of the scheme in the laboratory using feedback control is suggested.
Any real system, no matter how well isolated, unavoidably interacts with the environment. This interaction makes the evolution of a quantum system nonunitary and destroys the coherence of quantum superpositions. This process, known as decoherence, is widely regarded as the most important and fundamental obstacle to the practical realization of quantum information processing. On the other hand, the objectives of quantum control are predicated on the ability to manipulate the system coherently over a period of time. Quantum control has been applied successfully to several experimental systems and coupling such a controlled system to an environment makes the study of coherence loss possible. The standard model of decoherence is formulated in terms of a system, defined by the observables that can be measured, and a reservoir, de¯ned by those degrees of freedom that are not accessed by observation. The vibrational and rotational degree of freedom of diatomic molecules form an experimental model of such a system and bath 1. The nature of the ro-vibrational coupling does not allow a Decoherence Free Subspace, instead we try to identify a Decoherence Resistant Subspace using closed loop control. We set up a learning control loop experiment to monitor the coherence in a vibrational wavepacket, consisting of about 6 vibrational states of the A(1Σ+g ) electronic state, excited by a shaped, ultrashort optical pulse, and then to determine the pulse shape that yielded the longest coherence lifetime. The coherence of the vibrational wavepacket was monitored by measuring the fluorescence quantum beats from the outer turning point of the wave packet's trajectory. The closed loop controller altered the shape of the driving optical pulse to maximize the the depth of modulation of the quantum beats at a prescribed time after excitation, within the constraints of the laser system. The outcome of this closed loop control experiment shows an improvement of the beat decay constant of about 60%, as shown in Fig. (1), a result which occurs for several di®erent pulse shapes. Our experiments show that a number of interesting decoherence-resistant excitations exist. The nature of the dephasing was examined theoretically. Using measured optical pulse shapes, we simulated numerically the molecular wavepacket in the limit of perturbation theory. The experiment and simulations show that there are di®erent mechanisms contributing to the decoherence resistant excitation. The shaped pulse reduces the °uctuations in the wave packet spatial extent, which in turn changes the system reservoir coupling. Other components of the optimal pulse are a sequence of pulses that creates constructive interference of the vibrational wavepacket at the desired time, and chirp which compensates for the anharmonicity of the adiabatic potential. The experimental results show general agreement with numerical simulations. We conclude that wavepackets resistant to dephasing do exist,and that learning algorithms provide an effcient means for finding them.
In this paper, the problem of the decoherence of two\|state quantum systems interacting with a bath through an external controllable driving field is discussed. The time evolution of the off-diagonal elements of the density operator in two\|state quantum systems is obtained. The relation between the decoherence and the external controllable driving field is also obtained. Thus we establish the restriction equation that must be satisfied by the external controllable driving field when the decoherence is to vanish.
Keeping a quantum system in a given instantaneous eigenstate is a control problem with numerous applications, e.g., in quantum information processing. The problem is even more challenging in the setting of open quantum systems, where environment-mediated transitions introduce additional decoherence channels. Adiabatic passage is a well-established solution but requires a sufficiently slow evolution time that is dictated by the adiabatic theorem. Here we develop a systematic projection theory formulation for the transitionless evolution of general open quantum systems described by time-local master equations. We derive a time-convolutionless dynamical equation for the target instantaneous eigenstate of a given time-dependent Hamiltonian. A transitionless dynamics then arises in terms of a competition between the average Hamiltonian gap and the decoherence rate, which implies optimal adiabaticity timescales. We show how eigenstate tracking can be accomplished via control pulses, without explicitly incorporating counter-diabatic driving, thus offering an alternative route to accelerate adiabaticity. We examine rectangular pulses, chaotic signals, and white noise, and find that, remarkably, the effectiveness of eigenstate tracking hardly depends on the details of the control functions. In all cases the control protocol keeps the system in the desired instantaneous eigenstate throughout the entire evolution, along an accelerated adiabatic path.
Coherent control experiments in molecules are often done with shaped laser fields. The electric field is described classically and control over the time evolution of the system is achieved by shaping the laser pulses in the time or frequency domain. Moving on from a classical to a quantum description of the light field allows one to engineer the quantum state of light to steer chemical processes. The quantum field description of the photon mode allows one to manipulate the light-matter interaction directly in phase space. In this paper we demonstrate the basic principle of coherent control with quantum light on the avoided crossing in lithium fluoride. Using a quantum description of light together with the nonadiabatic couplings and vibronic degrees of freedoms opens up alternative perspective on quantum control. We show the deviations from control with purely classical light field and how back-action of the light field becomes important in a few-photon regime.
In molecules, electronic coherence typically decays within a few hundred femtoseconds, a timescale usually attributed to the environment. We show that it is set to a large extent by which coherences are excited: the molecule can host coherences that the bath barely sees, and optimal control can find and exploit them. Using gradient-based optimal control (GRAPE) with Redfield dynamics, we maximize the total vibronic coherence between the electronic ground and an optically bright electronic excited state in a three-state model with nonadiabatic features, in two regimes of low and high nonadiabatic mixing and for different system-bath coupling strengths. The Liouvillian spectrum reveals, in both regimes, a well-separated coherence mode with substantial ground-bright character that decays on a picosecond timescale. This mode is protected by mixing with the dark state, which brings the geometry of the optically accessible excited state close to that of the ground state and thus weakens its coupling to the bath. Without prior information, GRAPE finds this mode and keeps the photoexcited wave packet near the Franck-Condon region. At equal fluence, it increases the coherence at 800 fs by more than two orders of magnitude over a Gaussian pulse at the weakest coupling, and by many more at stronger coupling. The Liouvillian predicts the bath dependence of the long-lived coherence to within 1\%, and a Gaussian pulse tuned to the mode frequency comes within 10\% of the best pulse found. Beyond two-level and spin systems, our study puts forward the vibronic structure of molecules as a route to protected coherence subspaces, identifying a dark-state protection mechanism and a design criterion based on molecular parameters. These results lay the groundwork for our goal of using vibronic molecular systems as a resource for long-lived, controllable coherences in molecular quantum information science.