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- Englisch (46) (entfernen)
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- open quantum systems (2)
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Institut
- Wirtschaft und Informationstechnik Bocholt (46) (entfernen)
The two-state two-path model is introduced as a minimized model to describe the quantum dynamics of an electronic wave packet in the vicinity of a conical intersection. It involves two electronic potential energy surfaces each of which hosts a pair of quasi-classical trajectories over which the wave packet is assumed to be delocalized. When both trajectories evolve dynamically either diabatically or adiabatically, the full wave packet dynamics shows only features of the dynamics around avoided level crossings in the vicinity of the conical intersection. When one trajectory evolves adiabatically whereas the other trajectory follows a diabatic evolution, quantum mechanical interference of the wave packet components on each path generates Stueckelberg oscillations in the transition probability. These are surprisingly robust against a dissipative environment and, thus, should be a marker for conical intersections.
We study the nonequilibrium dynamics of a quantum system under the influence of two noncommuting fluctuation sources, i.e., purely dephasing fluctuations and relaxational fluctuations. We find that increasing purely dephasing fluctuations suppress increasing relaxation in the quantum system. This effect is further enhanced when both fluctuation sources are fully correlated. These effects arise for medium to strong primary fluctuations already when the secondary fluctuations are weak due to their noncommuting coupling to the quantum system. Dephasing, in contrast, is increased by increasing any of the two fluctuations. Fully correlated fluctuations result in overdamping at much lower system-bath coupling than uncorrelated noncommuting fluctuations. In total, we observe that treating subdominant secondary environmental fluctuations perturbatively leads, as neglecting them, to erroneous conclusions.
Tunneling two-level systems (TLSs) are ubiquitous in amorphous solids, and form a major source of noise in systems such as nano-mechanical oscillators, single electron transistors, and superconducting qubits. Occurance of defect tunneling despite their coupling to phonons is viewed as a hallmark of weak defect-phonon coupling. This is since strong coupling to phonons results in significant phonon dressing and suppresses tunneling in two-level tunneling defects effectively. Here we determine the dynamics of a tunneling defect in a crystal strongly coupled to phonons incorporating the full 3D geometry in our description. Wefind that inversion symmetric tunneling is not dressed by phonons whereas other tunneling pathways are dressed by phonons and, thus, are suppressed by strong defect-phonon coupling. We provide the linear acoustic and dielectric response functions for a tunneling defect in a crystal for strong defect-phonon coupling. This allows direct experimental determination of the defect-phonon coupling. The singling out of inversion-symmetric tunneling states in single tunneling defects is complementary to their dominance of the low energy excitations in strongly disordered solids as a result of inter-defect interactions for large defect concentrations. This suggests that inversion symmetric TLSs play a unique role in the low energy properties of disordered solids.
We show that strong non-Markovian effects can be revealed by the steady-state two-dimensional (2D) photon echo spectra at asymptotic waiting times. For this, we use a simple dimer toy model that is strongly coupled to a harmonic bath with parameters typical for photoactive biomolecules. We calculate the 2D photon echo spectra employing both the numerically exact hierarchy equation of motion and the quasiadiabatic path integral approach and compare these results with approximate results from a time-nonlocal quantum master equation approach. While the latter correctly reproduces the exact population dynamics at long times, it fails at the same time to correctly describe the 2D photon echo spectra at long waiting times. The differences show that non-Markovian effects are much more important for the steady-state 2D photon echoes than for the equilibrium populations. Thus, accurate theoretical descriptions of the energy transfer dynamics in biomolecular complexes have to be based on numerically exact simulations of the environmental fluctuations when nonlinear response functions are analyzed.
Ultrafast Energy Transfer in Excitonically Coupled Molecules Induced by a Nonlocal Peierls Phonon
(2019)
Molecular vibration can influence exciton transfer via either a local (intramolecular) Holstein or a nonlocal (intermolecular) Peierls mode. We show that a strong vibronic coupling to a nonlocal mode dramatically speeds up the transfer by opening an additional transfer channel. This Peierls channel is rooted in the formation of a conical intersection of the excitonic potential energy surfaces. For increasing Peierls coupling, the electronically coherent transfer for weak coupling turns into an incoherent transfer of a localized exciton through the intersection for strong coupling. The interpretation in terms of a conical intersection intuitively explains recent experiments of ultrafast energy transfer in photosynthetic and photovoltaic molecular systems.