Suppressing sampling noise in linear and two-dimensional spectral simulations.

We examine the problem of sampling noise encountered in time-domain simulations of linear and two-dimensional spectroscopies. A new adaptive apodization scheme based on physical arguments is devised for suppressing the noise in order to allow reducing the number of used disorder realisations, but introducing only a minimum of spectral aberrations and thus allowing a potential speed-up of these types of simulations. First, the method is demonstrated on an artificial dimer system, where the effect on slope analysis, typically used to study spectral dynamics, is analysed.

Surface hopping modeling of two-dimensional spectra.

Recently, two-dimensional (2D) electronic spectroscopy has become an important tool to unravel the excited state properties of complex molecular assemblies, such as biological light harvesting systems. In this work, we propose a method for simulating 2D electronic spectra based on a surface hopping approach. This approach self-consistently describes the interaction between photoactive chromophores and the environment, which allows us to reproduce a spectrally observable dynamic Stokes shift.