We present a novel joint time-dependent density-functional theory for the description of solute-solvent systems in time-dependent external potentials. Starting with the exact quantum-mechanical action functional for both electrons and nuclei, we systematically eliminate solvent degrees of freedom and thus arrive at coarse-grained action functionals which retain the highly accurate \emph{ab initio} description for the solute and are, in principle, exact. This procedure allows us to examine approximations underlying popular embedding theories for excited states. Finally, we introduce a novel approximate action functional for the solute-water system and compute the solvato-chromic shift of the lowest singlet excited state of formaldehyde in aqueous solution, which is in good agreement with experimental findings.
In recent years, hematite potential as a photoanode material for solar hydrogen production has ignited a renewed interest in its physical and interfacial properties, which continues to be an active field of research. Research on hematite photoanodes provides new insights on the correlations between electronic structure, transport properties, excited state dynamics and charge transfer phenomena, and expands our knowledge on solar cell materials into correlated electron systems. This research news article presents a snapshot of selected theoretical and experimental developments linking the elect…
Ultrafast Nonthermal Lattice Destabilization and Suppression of Polar Optical Scattering in Electronically Excited $α$-SiO$_2$ from First-Principles and Deep Neural Network Potential Modeling
The computation of excited electronic states with commonly employed (approximate) methods is challenging, typically yielding states of lower quality than the corresponding ground state for a higher computational cost. In this work, we present a mean field method that extends the previously proposed eXcited Constrained DFT (XCDFT) from single Slater determinants to ensemble 1-RDMs for computing low-lying excited states. The method still retains an associated computational complexity comparable to a semilocal DFT calculation while at the same time is capable of approaching states with multirefer…
Thermally activated delayed fluorescence (TADF) emitters consisting of donor and acceptor molecules are potentially highly interesting for electroluminescence (EL) applications. Their strong fluorescence emission is considered to be due to reverse intersystem crossing (RISC), in which energetically close triplet and singlet charge transfer (CT) states, also called exciplex states, are involved. In order to distinguish between different mechanisms and excited states involved, temperature-dependent spin-sensitive measurements on organic light-emitting diodes (OLEDs) and thin films are essential.…
Small molecule organic semiconductors hold great promise for efficient, printable, and flexible optoelectronic applications like solar cells and displays. However, strong excited-state quenching due to uncontrolled aggregation currently limits their performance and employability in devices. Here, we report on the self-assembly of a supramolecular pseudo-cube formed from six modified tetradentate perylene diimides (PDIs). The rigid, shape-persistent cage sets the distance and orientation of the PDI chromophores and suppresses intramolecular rotations and vibrations, leading to non-aggregated, m…
The emergence of transition metal dichalcogenides (TMD) as crystalline atomically thin semiconductors has created a tremendous amount of scientific and technological interest. Many novel device concepts have been proposed and realized (1-3). Nonetheless, progress in k-space investigations of ground/excited state electronic structures has been slow due to the challenge to create large scale, laterally homogeneous samples. Taking advantage of recent advancements in chemical vapor deposition, here we create a wafer-size MoS2 monolayer with well-aligned lateral orientation for advanced electron sp…
Triplet excited states in organic semiconductor materials and devices are notoriously difficult to detect and study with established spectroscopic methods. Yet, they are a crucial intermediate step in next-generation organic light emitting diodes (OLED) that employ thermally activated delayed fluorescence (TADF) to upconvert non-emissive triplets to emissive singlet states. In organic photovoltaic (OPV) devices, however, triplets are an efficiency-limiting exciton loss channel and are also involved in device degradation. Here, we introduce an innovative spin-sensitive method to study triplet s…
