We report how closely the Kohn−Sham highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) eigenvalues of 11 density functional theory (DFT) functionals, ...respectively, correspond to the negative ionization potentials (−IPs) and electron affinities (EAs) of a test set of molecules. We also report how accurately the HOMO−LUMO gaps of these methods predict the lowest excitation energies using both time-independent and time-dependent DFT (TD−DFT). The 11 DFT functionals include the local spin density approximation (LSDA), five generalized gradient approximation (GGA) functionals, three hybrid GGA functionals, one hybrid functional, and one hybrid meta GGA functional. We find that the HOMO eigenvalues predicted by KMLYP, BH&HLYP, B3LYP, PW91, PBE, and BLYP predict the −IPs with average absolute errors of 0.73, 1.48, 3.10, 4.27, 4.33, and 4.41 eV, respectively. The LUMOs of all functionals fail to accurately predict the EAs. Although the GGA functionals inaccurately predict both the HOMO and LUMO eigenvalues, they predict the HOMO−LUMO gap relatively accurately (∼0.73 eV). On the other hand, the LUMO eigenvalues of the hybrid functionals fail to predict the EA to the extent that they include HF exchange, although increasing HF exchange improves the correspondence between the HOMO eigenvalue and −IP so that the HOMO−LUMO gaps are inaccurately predicted by hybrid DFT functionals. We find that TD−DFT with all functionals accurately predicts the HOMO−LUMO gaps. A linear correlation between the calculated HOMO eigenvalue and the experimental −IP and calculated HOMO−LUMO gap and experimental lowest excitation energy enables us to derive a simple correction formula.
Atom transfer radical polymerization (ATRP) has become one of the most implemented methods for polymer synthesis, owing to impressive control over polymer composition and associated properties. ...However, contamination of the polymer by the metal catalyst remains a major limitation. Organic ATRP photoredox catalysts have been sought to address this difficult challenge but have not achieved the precision performance of metal catalysts. Here, we introduce diaryl dihydrophenazines, identified through computationally directed discovery, as a class of strongly reducing photoredox catalysts. These catalysts achieve high initiator efficiencies through activation by visible light to synthesize polymers with tunable molecular weights and low dispersities.
N-Aryl phenoxazines have been synthesized and introduced as strongly reducing metal-free photoredox catalysts in organocatalyzed atom transfer radical polymerization for the synthesis of well-defined ...polymers. Experiments confirmed quantum chemical predictions that, like their dihydrophenazine analogs, the photoexcited states of phenoxazine photoredox catalysts are strongly reducing and achieve superior performance when they possess charge transfer character. We compare phenoxazines to previously reported dihydrophenazines and phenothiazines as photoredox catalysts to gain insight into the performance of these catalysts and establish principles for catalyst design. A key finding reveals that maintenance of a planar conformation of the phenoxazine catalyst during the catalytic cycle encourages the synthesis of well-defined macromolecules. Using these principles, we realized a core substituted phenoxazine as a visible light photoredox catalyst that performed superior to UV-absorbing phenoxazines as well as previously reported organic photocatalysts in organocatalyzed atom transfer radical polymerization. Using this catalyst and irradiating with white LEDs resulted in the production of polymers with targeted molecular weights through achieving quantitative initiator efficiencies, which possess dispersities ranging from 1.13 to 1.31.
Predicting the stability of the perovskite structure remains a long-standing challenge for the discovery of new functional materials for many applications including photovoltaics and ...electrocatalysts. We developed an accurate, physically interpretable, and one-dimensional tolerance factor, τ, that correctly predicts 92% of compounds as perovskite or nonperovskite for an experimental dataset of 576
materials (
= O
, F
, Cl
, Br
, I
) using a novel data analytics approach based on SISSO (sure independence screening and sparsifying operator). τ is shown to generalize outside the training set for 1034 experimentally realized single and double perovskites (91% accuracy) and is applied to identify 23,314 new double perovskites (
) ranked by their probability of being stable as perovskite. This work guides experimentalists and theorists toward which perovskites are most likely to be successfully synthesized and demonstrates an approach to descriptor identification that can be extended to arbitrary applications beyond perovskite stability predictions.
Not a bit like his brother: DFT studies show that ammonia–borane dehydrogenations by iridium pincer complexes occur by concerted hydride and proton transfer from ammonia–borane to the catalyst, not ...through BH activation and subsequent β‐hydride elimination from the nitrogen end, as had been suggested. Such a concerted dehydrogenation pathway does not exist for ethane, which is isoelectronic with ammonia–borane.
Multi-exciton generation-the creation of multiple charge carrier pairs from a single photon-has been reported for several materials and may dramatically increase solar cell efficiency. Singlet ...fission, its molecular analogue, may govern multi-exciton generation in a variety of materials, but a fundamental mechanism for singlet fission has yet to be described. Here, we use sophisticated ab initio calculations to show that singlet fission in pentacene proceeds through rapid internal conversion of the photoexcited state into a dark state of multi-exciton character that efficiently splits into two triplets. We show that singlet fission to produce a pair of triplet excitons must involve an intermediate state that (i) has a multi-exciton character, (ii) is energetically accessible from the optically allowed excited state, and (iii) efficiently dissociates into multiple electron-hole pairs. The rational design of photovoltaic materials that make use of singlet fission will require similar ab initio analysis of multi-exciton states such as the dark state studied here.
A Correlated Electron View of Singlet Fission Zimmerman, Paul M; Musgrave, Charles B; Head-Gordon, Martin
Accounts of chemical research,
06/2013, Letnik:
46, Številka:
6
Journal Article
Recenzirano
Singlet fission occurs when a single exciton splits into multiple electron-hole pairs, and could dramatically increase the efficiency of organic solar cells by converting high energy photons into ...multiple charge carriers. Scientists might exploit singlet fission to its full potential by first understanding the underlying mechanism of this quantum mechanical process. The pursuit of this fundamental mechanism has recently benefited from the development and application of new correlated wave function methods. These methodscalled restricted active space spin flipcan capture the most important electron interactions in molecular materials, such as acene crystals, at low computational cost. It is unrealistic to use previous wave function methods due to the excessive computational cost involved in simulating realistic molecular structures at a meaningful level of electron correlation. In this Account, we describe how we use these techniques to compute single exciton and multiple exciton excited states in tetracene and pentacene crystals in order to understand how a single exciton generated from photon absorption undergoes fission to generate two triplets. Our studies indicate that an adiabatic charge transfer intermediate is unlikely to contribute significantly to the fission process because it lies too high in energy. Instead, we propose a new mechanism that involves the direct coupling of an optically allowed single exciton to an optically dark multiexciton. This coupling is facilitated by intermolecular motion of two acene monomers that drives nonadiabatic population transfer between the two states. This transfer occurs in the limit of near degeneracies between adiabatic states where the Born–Oppenheimer approximation of fixed nuclei is no longer valid. Existing theories for singlet fission have not considered this type of coupling between states and, therefore, cannot describe this mechanism. The direct mechanism through intermolecular motion describes many experimentally observed characteristics of these materials, such as the ultrafast time scale of photobleaching and triplet generation during singlet fission in pentacene. We believe this newly discovered mechanism provides fundamental insight to guide the creation of new solar materials that exhibit high efficiencies through multiple charge generation.
The Gibbs energy, G, determines the equilibrium conditions of chemical reactions and materials stability. Despite this fundamental and ubiquitous role, G has been tabulated for only a small fraction ...of known inorganic compounds, impeding a comprehensive perspective on the effects of temperature and composition on materials stability and synthesizability. Here, we use the SISSO (sure independence screening and sparsifying operator) approach to identify a simple and accurate descriptor to predict G for stoichiometric inorganic compounds with ~50 meV atom
(~1 kcal mol
) resolution, and with minimal computational cost, for temperatures ranging from 300-1800 K. We then apply this descriptor to ~30,000 known materials curated from the Inorganic Crystal Structure Database (ICSD). Using the resulting predicted thermochemical data, we generate thousands of temperature-dependent phase diagrams to provide insights into the effects of temperature and composition on materials synthesizability and stability and to establish the temperature-dependent scale of metastability for inorganic compounds.
Photoexcited intramolecular charge transfer (CT) states in N,N-diaryl dihydrophenazine photoredox catalysts are accessed through catalyst design and investigated through combined experimental studies ...and density functional theory (DFT) calculations. These CT states are reminiscent of the metal to ligand charge transfer (MLCT) states of ruthenium and iridium polypyridyl complexes. For cases where the polar CT state is the lowest energy excited state, we observe its population through significant solvatochromic shifts in emission wavelength across the visible spectrum by varying solvent polarity. We propose the importance of accessing CT states for photoredox catalysis of atom transfer radical polymerization lies in their ability to minimize fluorescence while enhancing electron transfer rates between the photoexcited photoredox catalyst and the substrate. Additionally, solvent polarity influences the deactivation pathway, greatly affecting the strength of ion pairing between the oxidized photocatalyst and the bromide anion and thus the ability to realize a controlled radical polymerization. Greater understanding of these photoredox catalysts with respect to CT and ion pairing enables their application toward the polymerization of methyl methacrylate for the synthesis of polymers with precisely tunable molecular weights and dispersities typically lower than 1.10.
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