Action-2D Electronic Spectroscopy is emerging as a powerful technique to investigate exciton dynamics in molecular aggregates and nanostructures. While maintaining the power of highlighting coherent evolution between the laser pulses,...

Action-detection has expanded the scope and applicability of 2D electronic spectroscopy, while posing new challenges for the unambiguous interpretation of spectral features. In this context, identifying the origin of cross-peaks at early waiting times is not trivial, and incoherent mixing is often invoked as an unwanted contribution masking the nonlinear signal. In this work, we elaborate on the relation between the nonlinear response and the incoherent mixing contribution by analyzing the action signal in terms of one- and two-particle observables. Considering a weakly interacting molecular dimer, we show how cross-peaks at early waiting times, reflecting exciton–exciton annihilation dynamics, can be equivalently interpreted as arising from incoherent mixing. This equivalence, on the one hand, highlights the information content of spectral features related to incoherent mixing and, on the other hand, provides an efficient numerical scheme to simulate the action response of weakly interacting systems.

Simulating charge and energy transfer in extended molecular networks requires an effective model to include the environment because it significantly affects the quantum dynamics. A prototypical effect known as Environment-Assisted Quantum Transport (ENAQT) consists in the enhancement of the transfer efficiency by the interaction with an environment. A simple description of this phenomenon is obtained by a quantum master equation describing a quantum walk over the molecular network in the presence of inter-site decoherence. We consider the problem of simulating the dynamics underlying ENAQT in a digital quantum computer. Two different quantum algorithms are introduced, the first one based on stochastic Hamiltonians and the second one based on a collision scheme. We test both algorithms by simulating ENAQT in a small molecular network on a quantum computer emulator and provide a comparative analysis of the two approaches. Both algorithms can be implemented in a memory efficient encoding with the number of required qubits scaling logarithmically with the size of the simulated system while the number of gates increases quadratically. We discuss the algorithmic quantum trajectories generated by the two simulation strategies showing that they realize distinct unravellings of the site-dephasing master equation. In our approach, the non-unitary dynamics of the open system is obtained through effective representations of the environment, paving the way to digital quantum simulations of quantum transport influenced by structured environments.

The theory of stochastic processes impacts both physical and social sciences. At the molecular scale, stochastic dynamics is ubiquitous because of thermal fluctuations. The Fokker-Plank-Smoluchowski equation models the time evolution of the probability density of selected degrees of freedom in the diffusive regime and it is a workhorse of physical chemistry. In this paper, we report the development and implementation of a Variational Quantum Eigensolver procedure to solve the Fokker-Planck-Smoluchowski eigenvalue problem. We show that such an algorithm, typically adopted to address quantum chemistry problems, can be applied effectively to classical systems paving the way to new applications of quantum computers. We compute the conformational transition rate in a linear chain of rotors experiencing nearest-neighbor interaction. We provide a method to encode on the quantum computer the probability distribution for a given conformation of the chain and assess its scalability in terms of operations. Performance analysis on noisy quantum emulators and quantum devices (IBMQ Santiago) is provided for a small chain showing results in good agreement with the classical benchmark without further addition of any error mitigation technique.