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QM/MM methods have been used to study electronic structure properties and chemical reactivity in complex molecular systems where direct electronic structure calculations are not feasible. In our previous work, we showed that non-polarizable force fields, by design, describe intermolecular interactions through pairwise interactions, overlooking many-body interactions involving three or more particles. In contrast, polarizable force fields account partially for many-body effects through polarization, but still handle van der Waals and permanent electrostatic interactions pairwise. We showed that despite those limitations, polarizable and non-polarizable force fields can reproduce relative cooperativity achieved using density functional theory due to error compensation mechanisms. In this contribution, we assess the performance of QM/MM methods in reproducing these phenomena. Our study highlights the significance of the QM region size and force field choice in QM/MM calculations, emphasizing the importance of parameter validation to obtain accurate interaction energy predictions. 

Abstract (Diene)Rh(I) complexes catalyze the stereoselective three‐component coupling of silyl glyoxylates, arylboronic acids, and aldehydes to give glycolate aldol products. The participation of Rh‐alkoxides in the requisite Brook rearrangement was established through two component Rh‐catalyzed couplings of silyl glyoxylates with ArB(OH)₂to give silyl‐protected mandelate derivatives. The intermediacy of a chiral Rh‐enolate was inferred through enantioselective protonation using a chiral Rh‐catalyst. Diastereoselective three‐component couplings with aldehydes as terminating electrophiles to give racemic products were best achieved with a bulky aryl ester on the silyl glyoxylate reagent. Optimal enantioselective couplings were carried out with thetert‐butyl ester variant using an anisole‐derived enantiopure tricyclo[3.2.2.0^2,4]nonadiene ligand. 

Newly developed fused-ring electron acceptors (FREAs) have proven to be an effective class of materials for extending the absorption window and boosting the efficiency of organic photovoltaics (OPVs). While numerous acceptors have been developed, there is surprisingly little structural diversity among high performance FREAs in literature. Of the high efficiency electron acceptors reported, the vast majority utilize derivatives of 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile (INCN) as the acceptor moiety. It has been postulated that the high electron mobility exhibited by FREA molecules with INCN end groups is a result of close π–π stacking between the neighboring planar INCN groups, forming an effective charge transport pathway between molecules. To explore this as a design rationale for electron acceptors, we synthesized a new fused-ring electron acceptor, IDTCF, which has methyl substituents out of plane to the conjugated acceptor backbone. These methyl groups hinder packing and expand the π–π stacking distance by ∼1 Å, but have little impact on the optical or electrochemical properties of the individual FREA molecule. The extra steric hindrance from the out of plane methyl substituents restricts packing and results in large amounts of geminate recombination, thus degrading the device performance. Our results show that intermolecular interactions (especially π–π stacking between end groups) play a crucial role in performance of FREAs. We demonstrated that the planarity of the acceptor unit is of paramount importance as even minor deviations in end group distance are enough to disrupt crystallinity and cripple device performance. 

In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022. 

Abstract The physics potential of detecting⁸B solar neutrinos will be exploited at the Jiangmen Underground Neutrino Observatory (JUNO), in a model-independent manner by using three distinct channels of the charged current (CC), neutral current (NC), and elastic scattering (ES) interactions. Due to the largest-ever mass of¹³C nuclei in the liquid scintillator detectors and the expected low background level,⁸B solar neutrinos are observable in the CC and NC interactions on¹³C for the first time. By virtue of optimized event selections and muon veto strategies, backgrounds from the accidental coincidence, muon-induced isotopes, and external backgrounds can be greatly suppressed. Excellent signal-to-background ratios can be achieved in the CC, NC, and ES channels to guarantee the observation of the⁸B solar neutrinos. From the sensitivity studies performed in this work, we show that JUNO, with 10 yr of data, can reach the 1σprecision levels of 5%, 8%, and 20% for the⁸B neutrino flux, ${\sin }^2{\theta }_{12}$, and $\mathrm{\Delta }{m}_{21}^2$, respectively. Probing the details of both solar physics and neutrino physics would be unique and helpful. In addition, when combined with the Sudbury Neutrino Observatory measurement, the world's best precision of 3% is expected for the measurement of the⁸B neutrino flux.