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Electronic Structure Tuning of Lanthanidocene Photocatalysts for C–F Bond Cleavage
A set of nine new robust, tunable cerium complexes supported by an ansa-bis(cyclopentadienyl) ligand, [Me 2 Si(η 5 -Cp R ) 2 ]CeX ( an Cp R )CeX, are excellent homogeneous visible-light photocatalysts for the monodefluoroalkylation of trifluorotoluene with Mg(CH 2 C 6 H 5 ) 2 THF 2 (R = Me 4 , SiMe 3 , X = N(SiMe 3 ) 2 (N″), X = CH(SiMe 3 ) 2 (R''), Cl, OC 6 H 2 t Bu 2 -2,6,Me-4 (OAr)). The trends in photocatalytic activity within the series are explained by photophysical spectroscopic analyses. The aryloxide complex [Me 2 Si(Cp SiMe3 ) 2 ]CeOAr, which has the highest activity (95% substrate conversion in 27 h), shows the most negative (most reducing) excited-state reduction potential (-2.71 V vs Fc). The precatalyst excited-state lifetimes are also exceptionally long. Detailed photoluminescence, NMR spectroscopic, and kinetic studies on chloride [Me 2 Si(Cp Me4 ) 2 ]CeCl suggest that the "ate" complex [{Me 2 Si(Cp Me4 ) 2 } 2 Ce III ClBn][MgBn] is the active catalyst in the alkylation reaction to form PhCF 2 CH 2 Ph with high selectivity over PhCF 2 H. Finally, the reaction rates are up to 30 times higher than previously reported for organometallic rare-earth photocatalysts for these Ce complexes and comparable to established Ir-based photoredox systems.
Electronic Structure of Anilinopyridinate-Supported Ru 2 5+ Paddlewheel Compounds
Not provided.
Designing in the Face of Uncertainty: Exploiting Electronic Structure and Machine Learning Models for Discovery in Inorganic Chemistry
Not Available
All-Electron Plane-Wave Electronic Structure Calculations
Not Available
The General Atomic and Molecular Electronic Structure System (GAMESS): Novel Methods on Novel Architectures
The primary focus of GAMESS over the last 5 years has been the development of new high-performance codes that are able to take effective and efficient advantage of the most advanced computer architectures, both CPU and accelerators. These efforts include employing density fitting and fragmentation methods to reduce the high scaling of well-correlated (e.g., coupled-cluster) methods as well as developing novel codes that can take optimal advantage of graphical processing units and other modern accelerators. Because accurate wave functions can be very complex, an important new functionality in GAMESS is the quasi-atomic orbital analysis, an unbiased approach to the understanding of covalent bonds embedded in the wave function. Finally, best practices for the maintenance and distribution of GAMESS are also discussed.
Slimmer Geminals For Accurate F12 Electronic Structure Models
The Slater-type F12 geminal length scales originally tuned for the second-order Mo̷ller-Plesset F12 method are too large for higher-order F12 methods formulated using the SP (diagonal fixed-coefficient spin-adapted) F12 ansatz. The new geminal parameters reported herein reduce the basis set incompleteness errors (BSIEs) of absolute coupled-cluster singles and doubles F12 correlation energies by a significant─and increase with the cardinal number of the basis─margin. The effect of geminal reoptimization is especially pronounced for the cc-pVXZ-F12 basis sets (specifically designed for use with F12 methods) relative to their conventional aug-cc-pVXZ counterparts. The BSIEs of relative energies are less affected, but substantial reductions can be obtained, especially for atomization energies and ionization potentials with the cc-pVXZ-F12 basis sets. The new geminal parameters are therefore recommended for all applications of high-order F12 methods, such as coupled-cluster F12 methods and transcorrelated F12 methods.
Benchmark Electronic Structure Calculations for H 3 O + (H 2 O) n , n = 0–5, Clusters and Tests of an Existing 1,2,3-Body Potential Energy Surface with a New 4-Body Correction
We report a revision of a previously developed many-body (up to 3-body inter- actions) CCSD(T)-based potential energy surface (PES) for the hydrated proton and its extension that incorporates a simple 4-body term for the hydronium-water-water-water interactions. The new PES is parametrized from and tested against new extensive benchmark CCSD(T) Complete Basis Set (CBS) estimates of the binding energies of H3O+(H2O)n clusters, n=0-5, which include all known to date low-lying energy isomers. We report the energetics, structures and harmonic frequencies of the hydronium-water clusters using the PES and compare them against the new benchmarks as well as other best available ab initio results. This critical comparison demonstrates the high accuracy of the new many-body hydronium-water PES.
Assessing Electronic Structure Methods for Long-Range Three-Body Dispersion Interactions: Analysis and Calculations on Well-Separated Metal Atom Trimers
Three-body dispersion interactions are much weaker than their two-body counterpart. However, their importance grows quickly as the number of interacting monomers rises. To explore the numerical performance of correlation methods for long-range three-body dispersion, we performed calculations on eight very simple dispersion-dominated model metal trimers: Na 3 , Mg 3 , Zn 3 , Cd 3 , Hg 3 , Cu 3 , Ag 3 , and Au 3 . One encouraging aspect is that relatively small basis sets of augmented triple-ζ size appear to be adequate for three-body dispersion in the long-range. Coupled cluster calculations were performed at high levels to assess MP3, CCSD, CCSD(T), empirical density functional theory dispersion (D3), and the many-body dispersion (MBD) approach. We found that the accuracy of CCSD(T) was generally significantly lower than for two-body interactions, with errors sometimes reaching 20% in the investigated systems, while CCSD and particularly MP3 were generally more erratic. MBD is found to perform better than D3 at large distances, whereas the opposite is true at shorter distances. When computing reference numbers for three-body dispersion, care should be taken to appropriately represent the effect of the connected triple excitations, which are significant in most cases and incompletely approximated by CCSD(T).
Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters
Not provided.
Electronic Structure and Excited-State Dynamics of Rylene–Tetrapyrrole Panchromatic Absorbers
Panchromatic absorbers have potential applications in molecular-based energy-conversion schemes. A prior porphyrin–perylene dyad (P-PMI, where “MI” denotes monoimide) coupled via an ethyne linker exhibits panchromatic absorption (350–700 nm) and a tetrapyrrole-like lowest singlet excited state with a relatively long singlet excited-state lifetime (τ S ) and increased fluorescence quantum yield (Φ f ) versus the parent porphyrin. To explore the extension of panchromaticity to longer wavelengths, three arrays have been synthesized: a chlorin–terrylene dyad (C-TMI), a bacteriochlorin–terrylene dyad (B-TMI), and a perylene–porphyrin–terrylene triad (PMI-P-TMI), where the terrylene, a π-extended homologue of perylene, is attached via an ethyne linker. Characterization of the spectra (absorption and fluorescence), excited-state properties (lifetime, yields, and rate constants of decay pathways), and molecular-orbital characteristics reveals unexpected subtleties. The wavelength of the red-region absorption band increases in the order C-TMI (705 nm) < PMI-P-TMI (749 nm) < B-TMI (774 nm), yet each array exhibits diminished Φ f and shortened τ S values. The PMI-P-TMI triad in toluene exhibits Φ f = 0.038 and τ S = 139 ps versus the all-perylene triad (PMI-P-PMI) for which Φ f = 0.26 and τ S = 2000 ps. The results highlight design constraints for auxiliary pigments with tetrapyrroles to achieve panchromatic absorption with retention of viable excited-state properties.