Charge Recombination in Phosphorescent Organic Light-Emitting Diode Host–Guest Systems through QM/MM Simulations

Host–guest systems are crucial for achieving high efficiency in most organic light-emitting diode (OLED) devices. However, charge recombination in such systems is poorly understood due to complicated molecular environment, making the rational design of host–guest systems difficult. In this article, we present a computational study of a phosphorescent OLED with 2,8-bis­(triphenylsilyl)­dibenzofuran (BTDF) as the host and <i>fac</i>-tris­(2-phenylpyridine) iridium (<i>fac</i>-Ir­(ppy)₃) as the guest, using a combined quantum mechanics/molecular mechanics (QM/MM) scheme. A new reaction coordinate is introduced to measure the electrostatic interactions between the host and guest molecules. Ionization potentials and electron affinities of the host show broader distributions as the host–guest interaction increases. On the basis of these distributions, we describe a molecular picture of charge recombination on the guest and find a direct charge trapping route for this system. Our results suggest several strategies for the design of more efficient host and guest combinations

Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry

We propose a calculation scheme that accelerates QM/MM simulations of solvated systems. This new approach is based on the adiabatic approximation whereby the solute degrees of freedom are separated from those of the solvent. More specifically, we assume that the solute electron density remains constant with respect to the relaxation of the solvent molecules. This allows us to achieve a dramatic speed-up of QM/MM calculations by discarding the slow self-consistent field cycle. We test this method by applying it to the calculation of the redox potential of aqueous transition metal ions. The root-mean-square deviation (RMSD) between the full solvation and adiabatic approximation is only 0.17 V. We find a RMSD from experimental values of 0.32 V for the adiabatic approximation as compared to 0.31 V for the full solvation model, so that the two methods are of essentially the same accuracy. Meanwhile, the adiabatic calculations are up to 10 times faster than the full solvation calculations, meaning that the method proposed here reduces the cost of QM/MM calculations while retaining the accuracy

Non-radiative deactivation of cytosine derivatives at elevated temperature

<p>In this work, we simulate the non-radiative deactivation process of three cytosine derivatives with known S0/S1 conical intersections (cytosine, 5-fluorocytosine and 5-methylcytosine). We use quantum chemistry methods to compute the potential energy profile of each derivatives and estimate the energy barrier height between the minimum of the S1 state and the conical intersection. Although the topology of the potential surface seems to play a role in the deactivation process, we show that the magnitude of the barrier is too high to explain the picosecond timescale reported for this reaction. Instead, rates in agreement with experiments are predicted only when incorporating dynamical factors via <i>ab-initio</i> molecular dynamics and a generalised master equation approach. In particular, we find that the energy fluctuations experienced by the system after photoexcitation are key to realistically model the relaxation dynamics. In gas phase, the cytosine derivatives remain vibrationally ‘hot’ for long after the excitation, raising the effective temperature of the system. We argue that it is this elevated temperature that allows for the crossing of the energy barrier. Further, we show that the reaction kinetics are not actually dominated by the conical intersection as it is enough for the system to find an avoided crossing.</p

Direct-Coupling O₂ Bond Forming a Pathway in Cobalt Oxide Water Oxidation Catalysts

We report a catalytic mechanism for water oxidation in a cobalt oxide cubane model compound, in which the crucial O–O bond formation step takes place by direct coupling between two Co^IV(O) metal oxo groups. Our results are based upon density functional theory (DFT) calculations and are consistent with experimental studies of the CoPi water oxidation catalyst. The computation of energetics and barriers for the steps leading up to and including the O–O bond formation uses an explicit solvent model within a hybrid quantum mechanics/molecular mechanics (QM/MM) framework, and captures the essential hydrogen-bonding effects and dynamical flexibility of this system

Electrostatic Effects at Organic Semiconductor Interfaces: A Mechanism for “Cold” Exciton Breakup

Exciton dissociation at organic semiconductor interfaces is an important process for the design of future organic photovoltaic (OPV) devices, but at present, it is poorly understood. On the one hand, exciton breakup is very efficient in many OPVs. On the other, electron–hole pairs generated by an exciton should be bound by Coulombic attraction, and therefore difficult to separate in materials of such low dielectric. In this paper, we highlight several electrostatic effects that appear commonly at organic/organic interfaces. Using QM/MM simulations, we demonstrate that the electric fields generated in this fashion are large enough to overcome typical electron–hole binding energies and thus explain the high efficiencies of existing OPV devices without appealing to the existence of nonthermal (“hot”) carrier distributions. Our results suggest that the classical picture of flat bands at organic/organic interfaces is only qualitatively correct. A more accurate picture takes into account the subtle effects of electrostatics on interfacial band alignment

Self-Attractive Hartree Decomposition: Partitioning Electron Density into Smooth Localized Fragments

Chemical bonding plays a central role in the description and understanding of chemistry. Many methods have been proposed to extract information about bonding from quantum chemical calculations, the majority of them resorting to molecular orbitals as basic descriptors. Here, we present a method called self-attractive Hartree (SAH) decomposition to unravel pairs of electrons directly from the electron density, which unlike molecular orbitals is a well-defined observable that can be accessed experimentally. The key idea is to partition the density into a sum of one-electron fragments that simultaneously maximize the self-repulsion and maintain regular shapes. This leads to a set of rather unusual equations in which every electron experiences self-attractive Hartree potential in addition to an external potential common for all the electrons. The resulting symmetry breaking and localization are surprisingly consistent with chemical intuition. SAH decomposition is also shown to be effective in visualization of single/multiple bonds, lone pairs, and unusual bonds due to the smooth nature of fragment densities. Furthermore, we demonstrate that it can be used to identify specific chemical bonds in molecular complexes and provides a simple and accurate electrostatic model of hydrogen bonding

Systematic Parametrization of Polarizable Force Fields from Quantum Chemistry Data

We introduce ForceBalance, a method and free software package for systematic force field optimization with the ability to parametrize a wide variety of functional forms using flexible combinations of reference data. We outline several important challenges in force field development and how they are addressed in ForceBalance, and present an example calculation where these methods are applied to develop a highly accurate polarizable water model. ForceBalance is available for free download at https://simtk.org/home/forcebalance

Prediction of Excited-State Energies and Singlet–Triplet Gaps of Charge-Transfer States Using a Restricted Open-Shell Kohn–Sham Approach

Organic molecules with charge-transfer (CT) excited states are widely used in industry and are especially attractive as candidates for fabrication of energy efficient OLEDs, as they can harvest energy from nonradiative triplets by means of thermally activated delayed fluorescence (TADF). It is therefore useful to have computational protocols for accurate estimation of their electronic spectra in order to screen candidate molecules for OLED applications. However, it is difficult to predict the photophysical properties of TADF molecules with LR-TDDFT, as semilocal LR-TDDFT is incapable of accurately modeling CT states. Herein, we study absorption energies, emission energies, zero–zero transition energies, and singlet–triplet gaps of TADF molecules using a restricted open-shell Kohn–Sham (ROKS) approach instead and discover that ROKS calculations with semilocal hybrid functionals are in good agreement with experimentsunlike TDDFT, which significantly underestimates energy gaps. We also propose a cheap computational protocol for studying excited states with large CT character that is found to give good agreement with experimental results without having to perform any excited-state geometry optimizations

Triplet vs Singlet Energy Transfer in Organic Semiconductors: The Tortoise and the Hare

Current bilayer organic photovoltaics cannot be made thick enough to absorb all incident solar radiation because of the short diffusion lengths (≈10 nm) of singlet excitons. Thus, the diffusion length sets an upper bound on the efficiency of these devices. By contrast, triplet excitons can have very long diffusion lengths (as large as 10 μm) in organic solids, leading some to speculate that triplet excitonic solar cells could be more efficient than their singlet counterparts. In this paper, we examine the nature of singlet and triplet exciton diffusion. We demonstrate that although there are fundamental physical upper bounds on the distance singlet excitons can travel by hopping, there are no corresponding limits on triplet diffusion lengths. This conclusion strongly supports the idea that triplet diffusion should be more controllable than singlet diffusion in organic photovoltaics. To validate our predictions, we model triplet diffusion by purely ab inito means in various crystals, achieving good agreement with experimental values. We further show that in at least one example (tetracene), triplet diffusion is fairly robust to disorder in thin films, as a result of the formation of semicrystalline domains and the high internal reorganization energy for triplet hopping. These results support the potential usefulness of triplet excitons in achieving maximum organic photovoltaic device efficiency

The Impact of Carrier Delocalization and Interfacial Electric Field Fluctuations on Organic Photovoltaics

Organic photovoltaic (OPV) devices hold a great deal of promise for the emerging solar market. However, to unlock this promise, it is necessary to understand how OPV devices generate free charges. Here, we analyze the energetics and charge delocalization of the interfacial charges in poly­(<i>p</i>-phenylenevinylene) (PPV)/[6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) and poly­(3-hexylthiophene-2,5-diyl) (P3HT)/PCBM devices. We find that, in the PPV system, the interface does not produce molecular disorder, but an interfacial electric field is formed upon the inclusion of environmental polarization that promotes charge separation. In contrast, the P3HT system shows a significant driving force for charge separation due to interfacial disorder confining the hole. However, this feature is overpowered by the polarization of the electronic environment, which generates a field that inhibits charge separation. In the two systems studied herein, electrostatic effects dominate charge separation, overpowering interfacially induced disorder. This suggests that, when balancing polymeric order with electrostratic effects, the latter should take priority