Frequency dispersed transient absorption spectra of dissolved perylene: A case study using the density matrix version of the MCTDH method

A theoretical scheme is presented to calculate non-linear optical spectra of molecules in solution. Starting with electronic structure calculations of the ground and excited state, a subset of vibrational coordinates exhibiting the largest Huang–Rhys factors is assigned. It is used to set up a model Hamiltonian for density matrix multi configurational time-dependent Hartree (MCTDH) calculations. The expression derived for the dissipative part of the equation of motion goes beyond the earlier used Lindblad-form. In order to calculate the non-linear response the electric field strength is introduced into the density matrix equations used to directly determine the polarization. The whole scheme is applied to perylene as a reference case.