Piotr de Silva

We introduce a density-dependent bonding descriptor that enables simultaneous visualization of both covalent and noncovalent interactions. The proposed quantity is tailored to reveal the regions of space, where the total electron density results from a strong overlap of shell, atomic, or molecular densities. We show that this approach is successful in describing a variety of bonding patterns as well as nonbonding contacts. The Density Overlap Regions Indicator (DORI) analysis is also exploited t

The basic design principle for emitters exhibiting thermally activated delayed fluorescence (TADF) is the minimization of the singlet-triplet gap. While typically this gap is positive, a possible inversion of states has been proposed as a pathway to improve the efficiency of organic light-emitting diodes. Despite the efforts to design such emitters, there are very few reports indicating that it is at all possible. We analyze the problem of the gap inversion from the perspective of the electronic

We introduce a simple quantum-mechanical model for thermally activated delayed fluorescence (TADF). The Hamiltonian is represented in the basis of four spin-mixed diabatic states representing pure charge transfer (CT) and local excitations (LE). The model predicts that it is possible to realize lowest-lying adiabatic singlet (S1) and triplet (T1) states with a small singlet–triplet gap, differing CT/LE contributions, and appreciable LE component in the S1 state. These characteristics can explain

Symmetric aqueous organic redox flow batteries (RFBs) are potentially an inexpensive, durable, and safe energy storage technology. Unlike normal asymmetric flow batteries, they are based on electrolytes that exist in at least three oxidation states and can undergo a minimum of two distinct redox processes. We compute the redox potentials of selected electrolytes, with the intent to understand how the interaction between the redox units affects the potentials. We find that electronic interaction

We introduce a new tool (single exponential decay detector: SEDD) to extract information about bonding and localization in atoms, molecules, or molecular assemblies. The practical evaluation of SEDD does not require any explicit information about the orbitals. The only quantity needed is the electron density (calculated or experimental) and its derivatives up to the second order.

One of the challenges in organic light-emitting diodes research is finding ways to increase device efficiency by making use of the triplet excitons that are inevitably generated in the process of electroluminescence. One way to do so is by thermally activated delayed fluorescence (TADF), a process in which triplet excitons undergo upconversion to singlet states, allowing them to relax radiatively. The discovery of this phenomenon has ensued a quest for new materials that are able to effectively

The recently introduced density overlap regions indicator (DORI) [P. de Silva and C. Corminboeuf, J. Chem. Theory Comput. 10(9), 3745-3756 (2014)] is a density-dependent scalar field revealing regions of high density overlap between shells, atoms, and molecules. In this work, we exploit its properties to construct local hybrid exchange-correlation functionals aiming at balanced reduction of the self-interaction error. We show that DORI can successfully replace the ratio of the von Weizsäcker and

Abstract Organic redox‐active battery materials are an emerging alternative to their inorganic counterparts currently used in the commercialized battery technologies. The main advantages of organic batteries are the potential for low‐cost manufacturing, tunability of electrochemical properties through molecular engineering, and their environmental sustainability. The search for organic electroactive materials that could be used for energy storage in mobile and stationary applications is an activ

Static and dynamic energetic disorder in emission layers of organic light-emitting diodes (OLEDs) is investigated through combined molecular dynamics and hybrid quantum mechanics/molecular mechanics (QM/MM) calculations. The analysis is based on a comparison of ensemble and time distributions of site energies of guest and host components in an emission layer. The law of total variance is applied to decompose the total disorder into its static and dynamic contributions. It is found that both cont

Graphite felt is a widely used electrode material for vanadium redox flow batteries. Electrode activation leads to the functionalization of the graphite surface with epoxy, OH, C=O, and COOH oxygenic groups and changes the carbon surface morphology and electronic structure, thereby improving the electrode's electroactivity relative to the untreated graphite. In this study, density functional theory (DFT) calculations are conducted to evaluate functionalization's contribution towards the positive

In methods based on frozen-density embedding theory or subsystem formulation of density functional theory, the non-additive kinetic potential (v(t)(nad)(r)) needs to be approximated. Since v(t)(nad)(r) is defined as a bifunctional, the common strategies rely on approximating v(t)(nad)[ρ(A),ρ(B)](r). In this work, the exact potentials (not bifunctionals) are constructed for chemically relevant pairs of electron densities (ρ(A) and ρ(B)) representing: dissociating molecules, two parts of a molecul

Within the linear combination of atomic orbitals (LCAO) approximation, one can distinguish two different Kohn-Sham potentials. One is the potential available numerically in calculations, and the other is the exact potential corresponding to the LCAO density. The latter is usually not available, but can be obtained from the total density by a numerical inversion procedure or, as is done here, analytically using only one LCAO Kohn-Sham orbital. In the complete basis-set limit, the lowest-lying Koh

Discovering new materials for energy storage requires reliable and efficient protocols for predicting key properties of unknown compounds. In the context of the search for new organic electrolytes for redox flow batteries, we present and validate a robust procedure to calculate the redox potentials of organic molecules at any pH value, using widely available quantum chemistry and cheminformatics methods. Using a consistent experimental data set for validation, we explore and compare a few differ

A dual-photofunctional organogermanium compound based on a donor-acceptor-donor architecture that exhibits thermally activated delayed fluorescence and mechano-responsive luminochromism has been developed. The developed compound was successfully applied as an emitter for efficient organic light-emitting diodes.

In addition to reverse intersystem crossing, triplet-to-singlet exciton transfers plays an important role in the triplet harvesting mechanism in hyperfluorescent organic light-emitting diodes.