Cluster-Based Approach Utilizing Optimally Tuned TD-DFT to Calculate Absorption Spectra of Organic Semiconductor Thin Films.

The photophysics of organic semiconductor (OSC) thin films or crystals has garnered significant attention in recent years since a comprehensive theoretical understanding of the various processes occurring upon photoexcitation is crucial for assessing the efficiency of OSC materials. To date, research in this area has relied on methods using Frenkel-Holstein Hamiltonians, calculations of the GW-Bethe-Salpeter equation with periodic boundaries, or cluster-based approaches using quantum chemical methods, with each of the three approaches having distinct advantages and disadvantages. In this work, we introduce an optimally tuned, range-separated time-dependent density functional theory approach to accurately reproduce the total and polarization-resolved absorption spectra of pentacene, tetracene, and perylene thin films, all representative OSC materials.

Adsorption Structures Affecting the Electronic Properties and Photoinduced Charge Transfer at Perylene-Based Molecular Interfaces.

Perylene-based organic semiconductors are widely used in organic electronic devices. Here, we studied the ultrafast excited state dynamics after optical excitation at interfaces between the electron donor (D) diindenoperylene (DIP) and the electron acceptor (A) dicyano-perylene-bis(dicarboximide) (PDIR-CN ) using femtosecond time-resolved second harmonic generation (SHG) in combination with large scale quantum chemical calculations. Thereby, we varied in bilayer structures of DIP and PDIR-CN the interfacial molecular geometry.

Accurate Polarization-Resolved Absorption Spectra of Organic Semiconductor Thin Films Using First-Principles Quantum-Chemical Methods: Pentacene as a Case Study.

Theoretical studies using clusters as model systems have been extremely successful in explaining various photophysical phenomena in organic semiconductor (OSC) thin films. But they have not been able to satisfactorily simulate total and polarization-resolved absorption spectra of OSCs so far. In this work, we demonstrate that accurate spectra are predicted by time-dependent density functional theory (TD-DFT) when the employed cluster reflects the symmetry of the crystal structure and all monomers feel the same environment.

Methylbismuth: an organometallic bismuthinidene biradical.

We report the generation, spectroscopic characterization, and computational analysis of the first free (non-stabilized) organometallic bismuthinidene, BiMe. The title compound was generated from BiMe by controlled homolytic Bi-C bond cleavage in the gas phase. Its electronic structure was characterized by a combination of photoion mass-selected threshold photoelectron spectroscopy and DFT as well as multi-reference computations.