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An in-depth theoretical analysis of key chemical equilibria in Signal Amplification by Reversible Exchange (SABRE) is provided, employing density functional theory calculations to characterize the likely reaction network. For all reactions in the network, the potential energy surface is probed to identify minimum energy pathways. Energy barriers and transition states are calculated, and harmonic transition state theory is applied to calculate exchange rates that approximate experimental values. The reaction network energy surface can be modulated by chemical potentials that account for the dependence on concentration, temperature, and partial pressure of molecular constituents (hydrogen, methanol, pyridine) supplied to the experiment under equilibrium conditions. We show that, under typical experimental conditions, the Gibbs free energies of the two key states involved in pyridine-hydrogen exchange at the common Ir-IMes catalyst system in methanol are essentially the same, i. e., nearly optimal for SABRE. We also show that a methanol-containing intermediate is plausible as a transient species in the process.

Signal Amplification By Reversible Exchange (SABRE) is a particularly simple hyperpolarisation approach. However, compared to other hyperpolarisation methods, SABRE is more limited in substrate scope. Therefore, it is critical to understand and overcome the factors limiting generalization. Past developments in SABRE catalyst optimization have emphasized large enhancements in the canonical SABRE substrate: pyridine and structurally closely related motifs. However, the pyridine-optimized catalysts are not efficient at hyperpolarising more sterically demanding substrates, including 2-substituted pyridine derivatives. Here we report that modifications of the catalyst ligand sphere, using a chelating ligand in particular, can increase the volume fraction available for substrate coordination to the iridium catalyst, thus permitting significant signal enhancements on otherwise sterically hindered substrates. The system yields (1)H enhancements on the order of 100-fold over 8.5 T thermal measurements for 2-substituted pyridine derivatives, and smaller, yet significant (1)H enhancement for provitamin B(6) and caffeine. For the 2-substituted pyridine derivatives we further show (15)N enhancements on the order of 1000-fold and (19)F enhancements of 30-fold over 8.5 T thermal polarisations.

Parahydrogen is an inexpensive and readily available source of hyperpolarization used to enhance magnetic resonance signals by up to four orders of magnitude above thermal signals obtained at ∼10 T. A significant challenge for applications is fast signal decay after hyperpolarization. Here we use parahydrogen-based polarization transfer catalysis at microtesla fields (first introduced as SABRE-SHEATH) to hyperpolarize 13C2 spin pairs and find decay time constants of 12 s for magnetization at 0.3 mT, which are extended to 2 min at that same field, when long-lived singlet states are hyperpolarized instead. Enhancements over thermal at 8.5 T are between 30 and 170 fold (0.02 to 0.12% polarization). We control the spin dynamics of polarization transfer by choice of microtesla field, allowing for deliberate hyperpolarization of either magnetization or long-lived singlet states. Density functional theory calculations and experimental evidence identify two energetically close mechanisms for polarization transfer...

Routine applications of electronic structure theory to molecules and periodic systems need to compute the electron density from given Hamiltonian and, in case of non-orthogonal basis sets, overlap matrices. System sizes can range from few to thousands or, in some examples, millions of atoms. Different discretization schemes (basis sets) and different system geometries (finite non-periodic vs. infinite periodic boundary conditions) yield matrices with different structures. The ELectronic Structure Infrastructure (ELSI) project provides an open-source software interface to facilitate the implementation and optimal use of high-performance solver libraries covering cubic scaling eigensolvers, linear scaling density-matrix-based algorithms, and other reduced scaling methods in between. In this paper, we present recent improvements and developments inside ELSI, mainly covering (1) new solvers connected to the interface, (2) matrix layout and communication adapted for parallel calculations of periodic and/or spin-polarized systems, (3) routines for density matrix extrapolation in geometry optimization and molecular dynamics calculations, and (4) general utilities such as parallel matrix I/O and JSON output. The ELSI interface has been integrated into four electronic structure code projects (DFTB+, DGDFT, FHI-aims, SIESTA), allowing us to rigorously benchmark the performance of the solvers on an equal footing. Based on results of a systematic set of large-scale benchmarks performed with Kohn–Sham density-functional theory and density-functional tight-binding theory, we identify factors that strongly affect the efficiency of the solvers, and propose a decision layer that assists with the solver selection process. Finally, we describe a reverse communication interface encoding matrix-free iterative solver strategies that are amenable, e.g., for use with planewave basis sets., This research was supported by the National Science Foundation (NSF), USA under Award No. 1450280. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy (DOE) Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. This research also used resources of the Argonne Leadership Computing Facility, a DOE, USA Office of Science User Facility supported under Contract No. DE-AC02-06CH11357. We appreciate the constructive feedback from many fellow researchers in the electronic structure community, including developers and users of the BigDFT, CP2K, DFTB+, DGDFT, FHI-aims, NTChem, SIESTA projects and of CECAM’s Electronic Structure Library project. Yu was additionally supported by a fellowship from the Molecular Sciences Software Institute under NSF, USA Award No. 1547580. García thanks EU H2020, European Union grant 824143 (“MaX: Materials at the eXascale” CoE), Spain’s AEI (PGC2018-096955-B-C44 and “Severo Ochoa” grant SEV-2015-0496), and GenCat, Spain 2017SGR1506.

The discovery of new materials as well as the determination of a vast set of materials properties for science and technology is a fast growing field of research, with contributions from many groups worldwide. Materials data from individual research groups is traditionally disseminated by means of loosely interconnected, peer-reviewed publications. MatD3 is an open-source, dedicated database and web application framework designed to store, curate and disseminate experimental and theoretical materials data generated by individual research groups or research consortia. A research group can set up its own instance of MatD3 and publish scientific results or simply use an existing online MatD3 instance. Disseminating research data in this form enables broader access, reproducibility, and repurposing of scientific products. MatD3 is a general purpose database that does not focus on any specific level of theory or experimental method. Instead, the focus is on storing and making accessible the data and making it straightforward to curate them.

Parahydrogen is an inexpensive and readily available source of hyperpolarization used to enhance magnetic resonance signals by up to 4 orders of magnitude above thermal signals obtained at ~10 T. A significant challenge for applications is fast signal decay after hyperpolarization. Here, we use parahydrogen based polarization transfer catalysis at micro-Tesla fields (first introduced as SABRE-SHEATH) to hyperpolarize 13C2 spin pairs and find decay time constants of 12 s for magnetization at 0.3 mT, which are extended to 2 minutes at that same field, when long-lived singlet states are hyperpolarized instead. Enhancements over thermal at 8.5 T are between 30 and 170 fold (0.02% to 0.12% polarization). We control the spin dynamics of polarization transfer by choice of μT field allowing for deliberate hyperpolarization of either magnetization or long-lived singlet states. Density functional theory (DFT) calculations and experimental evidence identify two energetically close mechanisms for polarization transfer: First, a model that involves direct binding of the 13C2 pair to the polarization transfer catalyst (PTC), and second, a model transferring polarization through auxiliary protons in substrates.

The analytical expressions for the three-dimensional spatial distribution of excitons and luminescence decay kinetics of wide band-gap crystals were derived taking into account the saturation effect for absorption near the centre of the incident laser beam with Gaussian transversal profile. The model is verified for the excitonic emission of CdWO4 crystals under excitation by ultra-short laser pulses in the region of weak excitonic absorption.

The full quasiparticle band structure of CdWO4 is calculated within the single-shot GW?(G0W0) approximation using maximally localized Wannier functions, which allows one to assess the validity of the commonly used scissor operator. Calculations are performed using the Godby?Needs plasmon pole model and the accurate contour deformation technique. It is shown that while the two methods yield identical band gap energies, the low-lying states are given inaccurately by the plasmon pole model. We report a band gap energy of 4.94?eV, including spin?orbit interaction at the DFT?LDA (density functional theory?local density approximation) level. Quasiparticle renormalization in CdWO4 is shown to be correlated with localization distance. Electron and hole effective masses are calculated at the DFT and G0W0 levels.

Nonlinear interaction of electronic excitations has been shown to play a remarkable role in luminescent material performance. Recently, it has been intensely studied in semiconductors and wide-gap scintillators. The nonlinear interaction is a cause of the nonproportionality of scintillator response to the energy of the absorbed ionizing radiation and can limit its energy resolution, which results in crucial deterioration of the scintillator functionality. The type and degree of nonproportionality are material specific and depend little on impurity content or sample treatment. Theoretical models have been developed, which explain the effect of scintillator response nonproportionality by the interplay between the density and mobility of charge carriers created in a track of ionizing radiation [1-3]. Energy losses in relaxation processes and the final distribution of excited luminescence centres in a material are determined by a number of processes including thermalisation of hot carriers, their recombination, interaction, trapping at defects and impurities and exciton formation. In the present contribution, we demonstrate how the mutual interaction of small-radius Frenkel excitons created at high densities by ionizing radiation or intense laser pulses can reveal itself in the luminescence characteristics of a luminescent material. It is shown that the related phenomena observed in various materials under X or γ rays are similar to those detected under UV-XUV excitation, which allows their theoretical description proceeding from the same principles and their experimental study in substantially better controlled experimental conditions of excitation by ultrashort laser pulses with well-defined timing and spatial parameters. A remarkable effect of saturation of excitonic absorption was discovered under excitation by ultrashort UV pulses from the energy region of phonon-assisted electronic transitions. The changes in the luminescence decay kinetics and various saturation effects in excitonic and impurity luminescence induced by high-density or high-energy excitation are demonstrated and theoretically modelled for several wide-gap materials. The experimental results of this contribution originate mainly from the study of time-resolved luminescence in tungstate crystals of different structures, wolframites CdWO4 and ZnWO4, and homologous scheelites CaWO4, SrWO4, BaWO4, by using femtosecond UV-XUV sources such as free-electron lasers, tuneable femtosecond lasers, high-order harmonic generation systems. It is shown that the emission decay and saturation can be described within the frame of Förster’s dipole-dipole interaction model on the basis of theoretical statements developed in [1]. The importance of studying exciton-exciton interactions is demonstrated by revealing a direct link between the Förster interaction radius and nonproportionality of the material light response. A good correlation between the radius of cation, radius of exciton and radius of Förster interaction is shown for the sequence of homologous scheelites CaWO4, SrWO4, BaWO4. References: A. N. Vasil’ev, IEEE Trans. Nucl. Sci. 55, 1054 (2008). G. Bizarri, W. W. Moses, J. Singh et al., J. Appl. Phys. 105, 044507 (2009). X. Lu, Q. Li, G. A. Bizarri et al., Phys. Rev. B 92, 115207 (2015).

Homologue scheelite crystals CaWO4, SrWO4, and BaWO4 possess similar crystal and electronic structure, but their luminescence exhibits drastically different thermal stabilities. By measuring the temperature dependence of the decay time of the intrinsic luminescence and fitting it to a three level model, we have qualitatively shown the effective exciton radius to increase in the order CaWO4 → SrWO4 → BaWO4, which explains the differences in the thermal stability. The origin of the variation in the exciton radii is suggested to be related to differences in the excited state dynamics in these crystals. From the decay kinetics measured under conditions of high excitation density, the efficiency of dipole-dipole interaction between excitons is shown to grow with exciton delocalization.

The decay kinetics of the excitonic emission of CdWO4 scintillators was studied under excitation by powerful 100 fs laser pulses in the band tail (Urbach) absorption region. A special imaging technique possessing both spatial and temporal resolution provided a unique insight into the Förster dipole-dipole interaction of self-trapped excitons, which is the main cause of the nonlinear quenching of luminescence in this material. In addition, the saturation of phonon-assisted excitonic absorption due to extremely short excitation pulses was discovered. A model describing the evolution of electronic excitations in the conditions of absorption saturation was developed and an earlier model of decay kinetics based on the Förster interaction was extended to include the saturation effect. Compared to the previous studies, a more accurate calculation yields 3.7 nm as the Förster interaction radius. It was shown that exciton-exciton interaction is the main source of scintillation nonproportionality in CdWO4. A quantitative description using a new model of nonproportionality was presented, making use of the corrected value of the Förster radius.