An efficient tool to calculate two-dimensional optical spectra for photoactive molecular complexes
(2015)

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.

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.