Hidden Phase of the Spin-Boson Model.

A quantum two-level system immersed in a sub-Ohmic bath experiences enhanced low-frequency quantum statistical fluctuations which render the nonequilibrium quantum dynamics highly non-Markovian. Upon using the numerically exact time-evolving matrix product operator approach, we investigate the phase diagram of the polarization dynamics. In addition to the known phases of damped coherent oscillatory dynamics and overdamped decay, we identify a new third region in the phase diagram for strong coupling showing an aperiodic behavior.

Intramolecular vibrations enhance the quantum efficiency of excitonic energy transfer.

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.

Dephasing and relaxational polarized sub-Ohmic baths acting on a two-level system.

We study a quantum two-level system under the influence of two independent baths, i.e., a sub-Ohmic pure dephasing bath and an Ohmic or sub-Ohmic relaxational bath.

Ultrafast Energy Transfer in Excitonically Coupled Molecules Induced by a Nonlocal Peierls Phonon.

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.

Spectroscopic Signatures of the Dynamical Hydrophobic Solvation Shell Formation.

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.

Quasi-adiabatic path integral approach for quantum systems under the influence of multiple non-commuting fluctuations.

Quantum systems are typically subject to various environmental noise sources. Treating these environmental disturbances with a system-bath approach beyond weak coupling, one must refer to numerical methods as, for example, the numerically exact quasi-adiabatic path integral approach. This approach, however, cannot treat baths which couple to the system via operators, which do not commute.

Nonequilibrium quantum solvation with a time-dependent Onsager cavity.

We formulate a theory of nonequilibrium quantum solvation in which parameters of the solvent are explicitly depending on time. We assume in a simplest approach a spherical molecular Onsager cavity with a time-dependent radius. We analyze the relaxation properties of a test molecular point dipole in a dielectric solvent and consider two cases: (i) a shrinking Onsager sphere and (ii) a breathing Onsager sphere.

Environmental rocking ratchet: Environmental rectification by a harmonically driven avoided crossing.

We propose a rocking ratchet designed as a symmetric quantum two-state system driven by a single periodic harmonic force and influenced symmetrically by thermal fluctuations. We show that the necessary broken symmetry can dynamically be achieved by a thermal environment that couples to the energy difference between the two states and the tunnel coupling between them. The quantum two-state system is driven by the harmonic periodic drive through its avoided crossing.

Two-dimensional photon echoes reveal non-Markovian energy transfer in an excitonic dimer.

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.

Nonequilibrium Response of Nanosystems Coupled to Driven Quantum Baths.

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.

Efficient tool to calculate two-dimensional optical spectra for photoactive molecular complexes.

We combine the coherent modified Redfield theory (CMRT) with the equation of motion-phase matching approach (PMA) to calculate two-dimensional photon-echo spectra for photoactive molecular complexes with an intermediate strength of the coupling to their environment. Both techniques are highly efficient, yet they involve approximations at different levels. By explicitly comparing with the numerically exact quasiadiabatic path integral approach, we show for the Fenna-Matthews-Olson complex that the CMRT describes the decay rates in the population dynamics well, but final stationary populations and the oscillation frequencies differ slightly.

Two-Dimensional Electronic Spectroscopy of Light-Harvesting Complex II at Ambient Temperature: A Joint Experimental and Theoretical Study.

We have performed broad-band two-dimensional (2D) electronic spectroscopy of light-harvesting complex II (LHCII) at ambient temperature. We found that electronic dephasing occurs within ∼60 fs and inhomogeneous broadening is approximately 120 cm(-1). A three-dimensional global fit analysis allows us to identify several time scales in the dynamics of the 2D spectra ranging from 100 fs to ∼10 ps and to uncover the energy-transfer pathways in LHCII.

Vibronically coherent speed-up of the excitation energy transfer in the Fenna-Matthews-Olson complex.

We show that underdamped molecular vibrations fuel the efficient excitation energy transfer in the Fenna-Matthews-Olson molecular aggregate under realistic physiological conditions. By employing an environmental fluctuation spectral function derived from experiments, we obtain numerically exact results for the exciton quantum dynamics in the presence of underdamped vibrationally coherent quantum states. Assuming the prominent 180-cm(-1) vibrational mode to be underdamped, additional coherent transport channels for the excitation energy transfer open up and we observe an increase of the transfer speed towards the reaction center by up to 24%.

Probing chirality fluctuations in molecules by nonlinear optical spectroscopy.

Symmetry breaking caused by geometric fluctuations can enable processes that are otherwise forbidden. An example is a perylene bisimide dyad whose dipole moments are perpendicular to each other. Förster-type energy transfer is thus forbidden at the equilibrium geometry since the dipolar coupling vanishes.

Cooling a magnetic nanoisland by spin-polarized currents.

We investigate cooling of a vibrational mode of a magnetic quantum dot by a spin-polarized tunneling charge current exploiting the magnetomechanical coupling. The spin-polarized current polarizes the magnetic nanoisland, thereby lowering its magnetic energy. At the same time, Ohmic heating increases the vibrational energy.

Hydration shell effects in the relaxation dynamics of photoexcited Fe-II complexes in water.

We study the relaxation dynamics of photoexcited Fe-II complexes dissolved in water and identify the relaxation pathway which the molecular complex follows in presence of a hydration shell of bound water at the interface between the complex and the solvent. Starting from a low-spin state, the photoexcited complex can reach the high-spin state via a cascade of different possible transitions involving electronic as well as vibrational relaxation processes. By numerically exact path integral calculations for the relaxational dynamics of a continuous solvent model, we find that the vibrational life times of the intermittent states are of the order of a few ps.

Quantification of non-Markovian effects in the Fenna-Matthews-Olson complex.

The excitation energy transfer dynamics in the Fenna-Matthews-Olson complex is quantified in terms of a non-Markovianity measure based on the time evolution of the trace distance of two quantum states. We use a system description derived from experiments and different environmental fluctuation spectral functions, which are obtained either from experimental data or from molecular dynamics simulations. These exhibit, in all cases, a nontrivial structure with several peaks attributed to vibrational modes of the pigment-protein complex.

Organic π-conjugated copolymers as molecular charge qubits.

We propose a design for molecular charge qubits based on π-conjugated block copolymers and determine their electronic structure as well as their vibrational active modes. By tuning the length of the oligomers, the tunnel coupling in the charge qubit and its decoherence properties due to molecular vibrations can be chemically engineered. Coherent oscillations result with quality factors of up to 10(4) at room temperature.

Noise-induced Förster resonant energy transfer between orthogonal dipoles in photoexcited molecules.

We show that Förster resonance energy transfer (FRET) in an orthogonally arranged donor-acceptor pair can be induced by environmental noise, although direct transfer is prohibited. Environmental fluctuations break the strict orthogonal dipole arrangement and cause effective fluctuating excitonic interactions. Using a scaling argument, we show that interaction fluctuations are coupled to those of the energy levels and are strong enough to induce large FRET rates.

Exciton transfer dynamics and quantumness of energy transfer in the Fenna-Matthews-Olson complex.

We present numerically exact results for the quantum coherent energy transfer in the Fenna-Matthews-Olson molecular aggregate under realistic physiological conditions, including vibrational fluctuations of the protein and the pigments for an experimentally determined fluctuation spectrum. We find coherence times shorter than observed experimentally. Furthermore, we determine the energy transfer current and quantify its "quantumness" as the distance of the density matrix to the classical pointer states for the energy current operator.

Multiphonon transitions in the biomolecular energy transfer dynamics.

We show that the biomolecular exciton dynamics under the influence of slow polarization fluctuations in the solvent cannot be described by lowest order, one-phonon approaches which are perturbative in the system-bath coupling. Instead, nonperturbative multiphonon transitions induced by the slow bath yield significant contributions. This is shown by comparing results for the decoherence rate of the exciton dynamics of a resumed perturbation theory with numerically exact real-time path-integral data.

Landau-Zener transitions in a dissipative environment: numerically exact results.

We study Landau-Zener transitions in a dissipative environment by means of the numerically exact quasiadiabatic propagator path integral. It allows to cover the full range of the involved parameters. We discover a nonmonotonic dependence of the transition probability on the sweep velocity which is explained in terms of a simple phenomenological model.

Memory effects in amorphous solids below 20 mK.

At temperatures below 1 K, the capacitance of a glass sample changes due to the application of a dc field in accordance with Burin's dipole gap theory [J. Low Temp. Phys.

Dynamics of the destruction and rebuilding of a dipole gap in glasses.

After a strong electric bias field is applied to the polyester glass Mylar at temperatures in the mK range, its dielectric constant increases and then decays logarithmically in time. We observed its dielectric response for several temperatures and different field sweeps. Starting from the dipole gap theory, we developed a model suggesting that the change in dielectric constant after transient application of a bias field is only partly due to relaxational processes.