Interplay between Intra- and Intermolecular Charge Transfer in the Optical Excitations of J-Aggregates
arXiv:1904.10730 · doi:10.1021/acs.jpcc.8b11709
Abstract
In a first-principles study based on density functional theory and many-body perturbation theory, we address the interplay between intra- and intermolecular interactions in a J-aggregate formed by push-pull organic dyes by investigating its electronic and optical properties. We find that the most intense excitation dominating the spectral onset of the aggregate, i.e., the J-band, exhibits a combination of intramolecular charge transfer, coming from the push-pull character of the constituting dyes, and intermolecular charge transfer, due to the dense molecular packing. We also show the presence of a pure intermolecular charge-transfer excitation within the J-band, which is expected to play a relevant role in the emission properties of the J-aggregate. Our results shed light on the microscopic character of optical excitations of J-aggregates and offer new perspectives to further understand the nature of collective excitations in organic semiconductors.
arXiv commentpublished under ACS Authorchoice license
References in corpus (16)
- Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
- Optimized norm-conserving Vanderbilt pseudopotentials
- Yambo: an \textit{ab initio} tool for excited state calculations
- Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange
- Implementation of an all-electron GW approximation based on the PAW method without plasmon pole approximation: application to Si, SiC, AlAs, InAs, NaH and KH
- Quasiparticle and Optical Spectroscopy of Organic Semiconductors Pentacene and PTCDA from First Principles
- Solid state effects on exciton states and optical properties of PPV
- Structural and excited-state properties of oligoacene crystals from first principles
- Origins of singlet fission in solid pentacene from an ab initio Green's-function approach
- Ab-initio prediction of the electronic and optical excitations in polythiophene: isolated chains versus bulk polymer
- Optical spectra from molecules to crystals: Insight from many-body perturbation theory
- Optical properties and charge-transfer excitations in edge-functionalized all-graphene nanojunctions
- Bound excitons and many-body effects in x-ray absorption spectra of azobenzene-functionalized self-assembled monolayers
- Optical properties of azobenzene-functionalized self-assembled monolayers: Intermolecular coupling and many-body interactions
- Solid-State Effects on the Optical Excitation of Push-Pull Molecular J-Aggregates by First-Principles Simulations
- Understanding effects of packing and chemical terminations on the optical excitations of azobenzene-functionalized self-assembled monolayers