Non-Perturbative Calculation of Two-Dimensional Spectra Using the Stochastic Hierarchy of Pure States

Two-dimensional electronic spectroscopy has become an important experimental technique to obtain information on, for example, electronic coherences in large molecular complexes or vibronic couplings. For the correct interpretation of two-dimensional spectra, however, detailed theoretical calculations are required. Reliable theoretical calculations are impeded by large system sizes and large numbers of vibrational degrees of freedom that need to be explicitly taken into account. Here, we demonstrate that a numerical approach based on a stochastic hierarchy of pure states (HOPS) does allow the calculation of two-dimensional spectra, notwithstanding the stochasticity of the method. The number of coupled equations as well as the hierarchy depth shows a superior scaling with system size as compared to the previously developed hierarchical equations of motion (HEOM). Large systems thus become accessible for numerical calculation of two-dimensional spectra.