Frank Schlawin

A comprehensive description of molecular electron transfer reactions is essential for our understanding of fundamental phenomena in bio-energetics and molecular electronics. Experimental studies of molecular systems in condensed-phase environments, however, face difficulties to independently control the parameters that govern the transfer mechanism with high precision. We show that trapped-ion experiments instead allow to reproduce and continuously connect vastly different regimes of molecular charge transfer through precise tuning of, e.g., phonon temperature, electron-phonon interactions, and electronic couplings. Such a setting allows not only to reproduce widely-used transport models, such as Marcus theory. It also provides access to transfer regimes that are unattainable for molecular experiments, while controlling and measuring the relevant observables on the level of individual quanta. Our numerical simulations predict an unconventional quantum transfer regime, featuring a transition from quantum adiabatic- to resonance-assisted transfer as a function of the donor-acceptor energy gap, that can be reached by increasing the electronic coupling at low temperatures. Trapped ion-based quantum simulations thus promise to enhance our microscopic understanding of molecular electron transfer processes, and may help to reveal efficient design principles for synthetic devices.

We devise a phase-coherent three-pulse protocol to probe the polariton dynamics in a trapped-ion quantum simulation. In contrast to conventional nonlinear signals, the presented scheme does not change the number of excitations in the system, allowing for the investigation of the dynamics within an $N$-excitation manifold. In the particular case of a filling factor one ($N$ excitations in an $N$-ion chain), the proposed interaction induces coherent transitions between a delocalized phonon superfluid and a localized atomic insulator phase. Numerical simulations of a two-ion chain demonstrate that the resulting two-dimensional spectra allow for the unambiguous identification of the distinct phases, and the two-dimensional lineshapes efficiently characterize the relevant decoherence mechanism.

Nonlinear spectroscopy employs a series of laser pulses to interrogate dynamics in large interacting many-body systems, and has become a highly successful method for experiments in chemical physics. Current quantum optical experiments approach system sizes and levels of complexity which require the development of efficient techniques to assess spectral and dynamical features with scalable experimental overhead. However, established methods from optical spectroscopy of macroscopic ensembles cannot be applied straightforwardly to few-atom systems. Based on the ideas proposed in [M. Gessner et al. New J. Phys. 16 092001 (2014)], we develop a diagrammatic approach to construct nonlinear measurement protocols for controlled quantum systems and discuss experimental implementations with trapped ion technology in detail. These methods in combination with distinct features of ultra-cold matter systems allow us to monitor and analyze excitation dynamics in both the electronic and vibrational degrees of freedom. They are independent of system size, and can therefore reliably probe systems where, e.g., quantum state tomography becomes prohibitively expensive. We propose signals that can probe steady state currents, detect the influence of anharmonicities on phonon transport, and identify signatures of chaotic dynamics near a quantum phase transition in an Ising-type spin chain.