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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.

When an open quantum system is driven by an external time-dependent force, the coupling of the driving to the central system is usually included, whereas the impact of the driving field on the bath is neglected. We investigate the effect of a quantum bath of linearly driven harmonic oscillators on the relaxation dynamics of a quantum two-level system which is not directly driven. In particular, we calculate the frequency-dependent response of the system when the bath is subject to Dirac and Gaussian driving pulses. We show that a time-retarded effective force on the system is induced by the driven bath which depends on the full history of the perturbation and the spectral characteristics of the underlying bath. In particular, when a structured Ohmic bath with a pronounced Lorentzian peak is considered, the dynamical response of the system to a driven bath is qualitatively different than that of the undriven bath. Specifically, additional resonances appear which can be directly associated with a Jaynes-Cummings-like effective energy spectrum.

Commonly, nanosystems are characterized by their response to time-dependent external fields in the presence of inevitable environmental fluctuations. The direct impact of the external driving on the environment is generally neglected. While this approach is satisfactory for macroscopic systems, on the nanoscale, an interaction of external fields with the environment is often unavoidable on principle. We extend the standard linear response theory of quantum dissipative systems to strongly driven baths. Significant modifications are found for two paradigm examples. First, we evaluate the polarizability of a molecule immersed in a strongly polarizable medium that responds to terahertz radiation. We find an increase of the molecular polarizability by about 30%. Second, we determine the response of a semiconductor quantum dot in close proximity to a metallic nanoparticle. Both are placed in a polarizable medium and exposed to electromagnetic irradiation. We show that the response of the quantum dot is qualitatively modified by the driven nanoparticle, including the generation of an additional channel of stimulated emission.

We present a scheme for cooling a vibrational mode of a magnetic molecular nanojunction by a spin-polarized charge current upon exploiting the interaction between its magnetic moment and the vibration. The spin-polarized charge current polarizes the magnetic moment of the nanoisland, thereby lowering its energy. A small but finite coupling between the vibration and the magnetic moment permits a direct exchange of energy such that vibrational energy can be transferred into the magnetic state. For positive bias voltages, this generates an effective cooling of the molecular vibrational mode. We determine parameter regimes for the cooling of the vibration to be optimal. Although the flowing charge current inevitably heats up the vibrational mode via Ohmic energy losses, we show that due to the magnetomechanical coupling, the vibrational energy (i.e, the effective phonon temperature) can be lowered below 50% of its initial value, when the two leads are polarized anti-parallel. In contrast to the cooling effect for positive bias voltages, net heating of the vibrational mode occurs for negative bias voltages. The cooling effect is enhanced for a stronger anti-parallel magnetic polarization of the leads, while the heating is stronger for a larger parallel polarization. Yet, dynamical cooling is also possible with parallel lead alignments when the two tunneling barriers are asymmetric.

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.

When a hydrophilic solute in water is suddenly turned into a hydrophobic species, for instance, by photoionization, a layer of hydrated water molecules forms around the solute on a time scale of a few picoseconds. We study the dynamic buildup of the hydration shell around a hydrophobic solute on the basis of a time-dependent dielectric continuum model. Information about the solvent is spectroscopically extracted from the relaxation dynamics of a test dipole inside a static Onsager sphere in the nonequilibrium solvent. The growth process is described phenomenologically within two approaches. First, we consider a time-dependent thickness of the hydration layer that grows from zero to a finite value over a finite time. Second, we assume a time-dependent complex permittivity within a finite layer region around the Onsager sphere. The layer is modeled as a continuous dielectric with a much slower fluctuation dynamics. We find a time-dependent frequency shift down to the blue of the resonant absorption of the dipole, together with a dynamically decreasing line width, as compared to bulk water. The blue shift reflects the work performed against the hydrogen-bonded network of the bulk solvent and is a directly measurable quantity. Our results are in agreement with an experiment on the hydrophobic solvation of iodine in water.

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.

We study the impact of underdamped intramolecular vibrational modes on the efficiency of the excitation energy transfer in a dimer in which each state is coupled to its own underdamped vibrational mode and, in addition, to a continuous background of environmental modes. For this, we use the numerically exact hierarchy equation of motion approach. We determine the quantum yield and the transfer time in dependence of the vibronic coupling strength, and in dependence of the damping of the incoherent background. Moreover, we tune the vibrational frequencies out of resonance with the excitonic energy gap. We show that the quantum yield is enhanced by up to 10% when the vibrational frequency of the donor is larger than at the acceptor. The vibronic energy eigenstates of the acceptor acquire then an increased density of states, which leads to a higher occupation probability of the acceptor in thermal equilibrium. We can conclude that an underdamped vibrational mode which is weakly coupled to the dimer fuels a faster transfer of excitation energy, illustrating that long-lived vibrations can, in principle, enhance energy transfer, without involving long-lived electronic coherence.