Mixing of Frenkel and charge-transfer excitons in quasi-one-dimensional one-component molecular crystals

TL;DR

This study models the mixing of Frenkel and charge-transfer excitons in quasi-one-dimensional molecular crystals, simulating their linear absorption spectra to better understand their spectral features and the role of exciton mixing.

Contribution

It introduces a vibronic model incorporating FE--CTEs mixing and applies it to simulate and analyze the absorption spectra of specific molecular crystals.

Findings

FE--CTEs mixing significantly influences the absorption spectra

Parameters fitted reproduce experimental spectral lineshapes

FE--CTEs mixing is essential for interpreting spectra of MePTCDI

Abstract

In molecular crystals like MePTCDI and PTCDA the molecule are regularly arranged creating quasi-one-dimensional molecular stacks. The intermolecular distance in a stack (about 3.3 A) is comparable with the electron--hole distance in the excited molecule. The mixing between Frenkel excitons (FEs) and charge-transfer excitons (CTEs) is very essential for the excitonic and vibronic spectra of both crystals. In this paper, we make simulations of the linear absorption spectra of the abovementioned crystals. The basic Hamiltonian describes the FE--CTEs mixing in the molecular stack (point group $C_i$) caused by two transfer mechanisms, notably of the electron and the hole on the neighbor molecules. The vibronic spectra consist of mixed excitons and one vibrational mode of an intramolecular vibration linearly coupled with FE and CTEs. Using the vibronic approach, we calculate the linear optical susceptibility in the excitonic and one-phonon vibronic regions of the molecular stack, as well as of a crystal which contains two types of nonequivalent stacks. We put the excitonic and vibrational parameters for the crystals of PTCDA and MePTCDI fitted in the previous studies. We analyze the general structure and some important features of the lineshape of the linear absorption spectra in the spectral region of 15 000--23000 cm^{-1}. We vary the values of the excitonic linewidth and the parameters of the linear exciton--phonon coupling and look for the values which reproduce the absorption lineshape similar to the absorption spectra of the investigated crystals. Our study exhibits the necessity of introducing the FE--CTEs mixing in the interpretation of the linear absorption spectra, especially of the MePTCDI crystal.