ABSTRACT
Multidimensional optical spectroscopies are powerful techniques to investigate energy transfer pathways in natural and artificial systems. Because of the high information content of the spectra, numerical simulations of the optical response are of primary importance to assist the interpretation of spectral features. However, the increasing complexity of the investigated systems and their quantum dynamics call for the development of novel simulation strategies. In this work, we consider using digital quantum computers. By combining quantum dynamical simulation and nonlinear response theory, we present a quantum algorithm for computing the optical response of molecular systems. The quantum advantage stems from the efficient quantum simulation of the dynamics governed by the molecular Hamiltonian, and it is demonstrated by explicitly considering exciton-vibrational coupling. The protocol is tested on a near-term quantum device, providing the digital quantum simulation of the linear and nonlinear response of simple molecular models.
ABSTRACT
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.
ABSTRACT
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 is based on measuring the incoherent signal proportional to the excited-state populations generated by an additional laser pulse. Numerical simulations of the action signal play a crucial role in aiding the interpretation of the spectral features, which may differ from those of the analog coherent technique in a non-trivial way. We present a numerical investigation of the action response of a model of quantum dot as a case study to unravel the exciton and biexciton contributions in the 2D-spectra of nanostructures. The simulation protocol is based on a non-perturbative treatment of the light-matter interaction by solving the Lindblad quantum master equation and the different contributions to the non-linear response are disentangled using a phase-modulation scheme. We analyze how the relative weights of the exciton and biexciton signals determine the lineshape of the spectrum, how they depend upon the physical nature of the detected signal, i.e., fluorescence or photocurrent, and on the relaxation dynamics during the detection-time. Compatibly with the experimental conditions, the choice of the detection-mode and the use of time-gating may eventually facilitate the evaluation of relevant parameters, such as the biexciton binding energy and the timescale of the biexciton relaxation.