Hydration shell effects in the relaxation dynamics of photoexcited Fe-II complexes in water
P. Nalbach, A. J. A. Achner, M. Frey, M. Grosser, C. Bressler, M. Thorwart
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. Since the electronic rearrangement in the complex occurs on the time scale of about 100 fs, we find that the complex first rearranges itself in a high-spin and highly excited vibrational state, before it relaxes its energy to the solvent via vibrational relaxation transitions. By this, the relaxation pathway can be clearly identified. We find that the life time of the vibrational states increases with the size of the complex (within a spherical model), but decreases with the thickness of the hydration shell, indicating that the hydration shell acts as an additional source of fluctuations.
Photon-assisted confinement-induced resonances for ultracold atoms
V. Leyton, M. Roghani, V. Peano, M. Thorwart
We solve the two-particle s-wave scattering for an ultracold-atom gas confined in a quasi-one-dimensional trapping potential which is periodically modulated. The interaction between the atoms is included via Fermi’s pseudopotential. For a modulated isotropic transverse harmonic confinement, the atomic center of mass and relative degrees of freedom decouple and an exact solution is possible. The modulation opens additional photon-assisted resonant scattering channels. Applying the Bethe-Peierls boundary condition, we obtain the general scattering solution of the time-dependent Floquet-Schrödinger equation which is universal at low energies. The effective one-dimensional scattering length can be controlled by the external driving.
Quantification of non-Markovian effects in the Fenna-Matthews-Olson complex
C. Mujica-Martinez, P. Nalbach, M. Thorwart
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. Such a structured environmental spectrum can, in principle, give rise to strong non-Markovian effects. We present numerically exact real-time path-integral calculations for the transfer dynamics and find, in all cases, a monotonic decrease of the trace distance with increasing time which renders a Markovian description valid.
Nonequilibrium quantum fluctuation relations for harmonic systems in nonthermal environments
D. Pagel, P. Nalbach, A. Alvermann, H. Fehske, M. Thorwart
We formulate exact generalized nonequilibrium fluctuation relations for the quantum mechanical harmonic oscillator coupled to multiple harmonic baths. Each of the different baths is prepared in its own individual (in general nonthermal) state. Starting from the exact solution for the oscillator dynamics we study fluctuations of the oscillator position as well as of the energy current through the oscillator under general nonequilibrium conditions. In particular, we formulate a fluctuation–dissipation relation for the oscillator position autocorrelation function that generalizes the standard result for the case of a single bath at thermal equilibrium. Moreover, we show that the generating function for the position operator fulfils a generalized Gallavotti–Cohen-like relation. For the energy transfer through the oscillator, we determine the average energy current together with the current fluctuations. Finally, we discuss the generalization of the cumulant generating function for the energy transfer to nonthermal bath preparations.
Crossover from coherent to incoherent quantum dynamics due to sub-Ohmic dephasing
P. Nalbach, M. Thorwart
We report exact results for the influence of purely sub-Ohmic dephasing on the dynamics of a quantum two-level system. From response functions, we determine a crossover coupling strength between oscillatory coherent and overdamped dynamics. Surprisingly, we find no overdamping even at arbitrary large dephasing for spectra with spectral exponent.
Organic pi-conjugated copolymers as molecular charge qubits
C. A. Mujica-Martinez, P. Nalbach, M. Thorwart
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 104 at room temperature. In turn, the molecular vibrational spectrum induces strong non-Markovian electronic effects which support the survival of quantum coherence.
Noise-Induced Förster Resonant Energy Transfer between Orthogonal Dipoles in Photoexcited Molecules
P. Nalbach, I. Pugliesi, H. Langhals, M. Thorwart
Quantum noise properties of multiphoton transitions in driven nonlinear resonators
V. Leyton, V. Peano, M. Thorwart
We investigate the quantum noise properties of a weakly nonlinear Duffing resonator in the deep quantum regime, where only a few quanta are excited. This regime is dominated by the appearance of coherent multiphoton resonances in the nonlinear response of the resonator to the modulation. We determine simple expressions for the photon noise spectrum and find that the multiphoton resonances also induce a multiple peak structure in that spectrum. When the corresponding multiphoton Rabi oscillations are underdamped, zero-temperature quantum fluctuations determine comparable populations of all quasienergy states which belong to a resonant multiphoton doublet. Most interestingly, the quantum fluctuations probe the multiphoton transitions by inducing several peaks in the noise spectrum of the resonator observables. In particular, the noise of the photon number contains complete information about the multiphoton states and their stationary populations via pairs of nearly symmetric peaks at opposite frequencies. Their widths are determined by the damping of the Rabi oscillations and their heights are proportional to the stationary nonequilibrium populations. A finite detuning from a multiphoton resonance generates a quasielastic noise peak at zero frequency. In addition, we relate the stationary populations of the quasienergy states with an effective quantum temperature and discuss the role of a finite temperature.