Non-radiative decay and stability of NN-heterocyclic carbene iridium(III) complexes

Devices based on deep-blue emitting iridium (III) complexes with N-heterocyclic carbene (NHC) ligands have recently been shown to give excellent performance as phosphorescent organic light-emitting diodes (PHOLEDs). To facilitate the design of even better deep-blue phosphorescent emitters we carried out density functional theory (DFT) calculations of the lowest triplet ($T_1$) potential-energy surfaces (PES) upon lengthening the iridium-ligand (Ir-C) bonds. Relativistic time dependent-DFT (TDDFT) calculations demonstrate that this changes the nature of $T_1$ from a highly-emissive metal-to-ligand charge transfer ($^3$MLCT) state to a metal centered ($^3$MC) state where the radiative decay rate is orders of magnitude slower than that of the $^3$MLCT state. We identify the elongation of an Ir-C bond on the NHC group as the pathway with lowest energy barrier between the $^3$MLCT and $^3$MC states for all complexes studied and show that the barrier height is correlated with the experimentally measured non-radiative decay rate. This suggests that the thermal population of $^3$MC states is the dominant non-radiative decay mechanism at room temperature. We show that the $^3$MLCT $\rightarrow$ $^3$MC transition is reversible, in marked contrast to other deep blue phosphors containing coordinating nitrogen atoms, where the population of $^3$MC states breaks Ir-N bonds. This suggests that, as well as improved efficiency, blue PHOLEDs containing phosphors where the metal is only coordinated by carbon atoms will have improved device lifetimes.Comment: 15 pages, 4 figures, 3 table

The emergence of 4-cycles in polynomial maps over the extended integers

Let $f(x) \in \mathbb{Z}[x]$; for each integer $\alpha$ it is interesting to consider the number of iterates $n_{\alpha}$, if possible, needed to satisfy $f^{n_{\alpha}}(\alpha) = \alpha$. The sets $\{\alpha, f(\alpha), \ldots, f^{n_{\alpha} - 1}(\alpha), \alpha\}$ generated by the iterates of $f$ are called cycles. For $\mathbb{Z}[x]$ it is known that cycles of length 1 and 2 occur, and no others. While much is known for extensions to number fields, we concentrate on extending $\mathbb{Z}$ by adjoining reciprocals of primes. Let $\mathbb{Z}[1/p_1, \ldots, 1/p_n]$ denote $\mathbb{Z}$ extended by adding in the reciprocals of the $n$ primes $p_1, \ldots, p_n$ and all their products and powers with each other and the elements of $\mathbb{Z}$. Interestingly, cycles of length 4, called 4-cycles, emerge for polynomials in $\mathbb{Z}\left[1/p_1, \ldots, 1/p_n\right][x]$ under the appropriate conditions. The problem of finding criteria under which 4-cycles emerge is equivalent to determining how often a sum of four terms is zero, where the terms are $\pm 1$ times a product of elements from the list of $n$ primes. We investigate conditions on sets of primes under which 4-cycles emerge. We characterize when 4-cycles emerge if the set has one or two primes, and (assuming a generalization of the ABC conjecture) find conditions on sets of primes guaranteed not to cause 4-cycles to emerge.Comment: 14 pages, 1 figur

When Does Spatial Diversification Usefully Maximize the Durability of Crop Disease Resistance?

Maximizing the durability of crop disease resistance genes in the face of pathogen evolution is a major challenge in modern agricultural epidemiology. Spatial diversification in the deployment of resistance genes, where susceptible and resistant fields are more closely intermixed, is predicted to drive lower epidemic intensities over evolutionary timescales. This is due to an increase in the strength of dilution effects, caused by pathogen inoculum challenging host tissue to which it is not well-specialized. The factors that interact with and determine the magnitude of this spatial suppressive effect are not currently well understood, however, leading to uncertainty over the pathosystems where such a strategy is most likely to be cost-effective. We model the effect on landscape scale disease dynamics of spatial heterogeneity in the arrangement of fields planted with either susceptible or resistant cultivars, and the way in which this effect depends on the parameters governing the pathosystem of interest. Our multiseason semidiscrete epidemiological model tracks spatial spread of wild-type and resistance-breaking pathogen strains, and incorporates a localized reservoir of inoculum, as well as the effects of within and between field transmission. The pathogen dispersal characteristics, any fitness cost(s) of the resistance-breaking trait, the efficacy of host resistance, and the length of the timeframe of interest all influence the strength of the spatial diversification effect. A key result is that spatial diversification has the strongest beneficial effect at intermediate fitness costs of the resistance-breaking trait, an effect driven by a complex set of nonlinear interactions. On the other hand, however, if the resistance-breaking strain is not fit enough to invade the landscape, then a partially effective resistance gene can result in spatial diversification actually worsening the epidemic. These results allow us to make general predictions of the types of system for which spatial diversification is most likely to be cost-effective, paving the way for potential economic modeling and pathosystem specific evaluation. These results highlight the importance of studying the effect of genetics on landscape scale spatial dynamics within host-pathogen disease systems.[Formula: see text] Copyright © 2020 The Author(s). This is an open access article distributed under the CC BY 4.0 International license

Audits and inspections are never enough: a critique to enhance food safety

Internal and external food safety audits are conducted to assess the safety and quality of food including on-farm production, manufacturing practices, sanitation, and hygiene. Some auditors are direct stakeholders that are employed by food establishments to conduct internal audits, while other auditors may represent the interests of a second party purchaser or a third-party auditing agency. Some buyers conduct their own audits or additional testing, while some buyers trust the results of third-party audits or inspections. Third-party auditors, however, use various food safety audit standards and most do not have a vested interest in the products being sold. Audits are conducted under a proprietary standard, while food safety inspections are generally conducted within a legal framework. There have been many foodborne illness outbreaks linked to food processors that have passed third-party audits and inspections, raising questions about the utility of both. Supporters argue third-party audits are a way to ensure food safety in an era of dwindling economic resources. Critics contend that while external audits and inspections can be a valuable tool to help ensure safe food, such activities represent only a snapshot in time. This paper identifies limitations of food safety inspections and audits and provides recommendations for strengthening the system, based on developing a strong food safety culture, including risk-based verification steps, throughout the food safety system

Efficient Adaptive Stochastic Collocation Strategies for Advection-Diffusion Problems with Uncertain Inputs

Physical models with uncertain inputs are commonly represented as parametric partial differential equations (PDEs). That is, PDEs with inputs that are expressed as functions of parameters with an associated probability distribution. Developing efficient and accurate solution strategies that account for errors on the space, time and parameter domains simultaneously is highly challenging. Indeed, it is well known that standard polynomial-based approximations on the parameter domain can incur errors that grow in time. In this work, we focus on advection-diffusion problems with parameter-dependent wind fields. A novel adaptive solution strategy is proposed that allows users to combine stochastic collocation on the parameter domain with off-the-shelf adaptive timestepping algorithms with local error control. This is a non-intrusive strategy that builds a polynomial-based surrogate that is adapted sequentially in time. The algorithm is driven by a so-called hierarchical estimator for the parametric error and balances this against an estimate for the global timestepping error which is derived from a scaling argument.Comment: 29 pages, 14 figure

Effect of n-propyl substituents on the emission properties of blue phosphorescent iridium(iii) complexes

Ligand substitution is often used for tuning the emission color of phosphorescent iridium(iii) complexes that are used in organic light-emitting diodes. However, in addition to tuning the emission color, the substituents can also affect the radiative and non-radiative decay rates of the excited state and hence the photoluminescence quantum yield. Understanding the substituent effect is therefore important for the design of new iridium(iii) complexes with specific emission properties. Using (time dependent) density functional methods, we investigate the substituent effect of n-propyl groups on the structure, emission color, and emission efficiency of fac-tris(1-methyl-5-phenyl-[1,2,4]triazolyl)iridium(iii) based phosphorescent complexes by comparing the calculated results for structural models with and without the n-propyl substituents. We find that attachment of the n-propyl groups increases the length of three Ir–N bonds, and although the emission color does not change significantly, the radiative and non-radiative rates do, leading to a prediction of enhanced blue phosphorescence emission efficiency. Furthermore, the calculations show that the attachment of the n-propyl groups leads to a larger activation energy to degradation and the formation of dark states

Gate control of Mott metal-insulator transition in a 2D metal-organic framework

Strong electron-electron Coulomb interactions in materials can lead to a vast range of exotic many-body quantum phenomena, including Mott metal-insulator transitions, magnetic order, quantum spin liquids, and unconventional superconductivity. These many-body phases are strongly dependent on band occupation and can hence be controlled via the chemical potential. Flat electronic bands in two-dimensional (2D) and layered materials such as the kagome lattice, enhance strong electronic correlations. Although theoretically predicted, correlated-electron phases in monolayer 2D metal-organic frameworks (MOFs) - which benefit from efficient synthesis protocols and tunable properties - with a kagome structure have not yet been realised experimentally. Here, we synthesise a 2D kagome MOF comprised of 9,10-dicyanoanthracene molecules and copper atoms on an atomically thin insulator, monolayer hexagonal boron nitride (hBN) on Cu(111). Scanning tunnelling microscopy (STM) and spectroscopy reveal an electronic energy gap of ~200 meV in this MOF, consistent with dynamical mean-field theory predictions of a Mott insulating phase. By tuning the electron population of kagome bands, via either template-induced (via local work function variations of the hBN/Cu(111) substrate) or tip-induced (via the STM probe) gating, we are able to induce Mott metal-insulator transitions in the MOF. These findings pave the way for devices and technologies based on 2D MOFs and on electrostatic control of many-body quantum phases therein.Comment: 19 pages, 4 figure

Interplay of zero-field splitting and excited state geometry relaxation in fac-Ir(ppy)3

The lowest energy triplet state, T-1, of organometallic complexes based on iridium(III) is of fundamental interest, as the behavior of molecules in this state determines the suitability of the complex for use in many applications, e.g., organic light-emitting diodes. Previous characterization of T-1 in fac-Ir(ppy)(3) suggests that the trigonal symmetry of the complex is weakly broken in the excited state. Here we report relativistic time dependent density functional calculations of the zero-field splitting (ZFS) of fac-Ir(ppy)(3) in the ground state (S-0) and lowest energy triplet (T-1) geometries and at intermediate geometries. We show that the energy scale of the geometry relaxation in the T-1 state is large compared to the ZFS. Thus, the natural analysis of the ZFS and the radiative decay rates, based on the assumption that the structural distortion is a small perturbation, fails dramatically. In contrast, our calculations of these quantities are in good agreement with experiment