Jensenpadgett3663

Our recently presented range-separated (RS) double-hybrid (DH) time-dependent density functional approach [J. Chem. Theory Comput. 17, 927 (2021)] is combined with spin-scaling techniques. The proposed spin-component-scaled (SCS) and scaled-opposite-spin (SOS) variants are thoroughly tested for almost 500 excitations including the most challenging types. This comprehensive study provides useful information not only about the new approaches but also about the most prominent methods in the DH class. The benchmark calculations confirm the robustness of the RS-DH ansatz, while several tendencies and deficiencies are pointed out for the existing functionals. Our results show that the SCS variant consistently improves the results, while the SOS variant preserves the benefits of the original RS-DH method reducing its computational expenses. It is also demonstrated that, besides our approaches, only the nonempirical functionals provide balanced performance for general applications, while particular methods are only suggested for certain types of excitations.The mechanism of the calcium-catalyzed coupling of alcohols with vinylboronic acids has been analyzed by means of density functional theory computations. This study reveals that the calcium and boron Lewis acids associate to form a superelectrophile able to promote a pericyclic group transfer reaction with allyl alcohols. With other alcohols, the two Lewis acids act synergistically to activate the OH functionality and trigger a SNi reaction pathway. These two mechanisms are affected by the nature of the counterions, which has been rationalized by electronic and steric factors.Water chlorination can lead to the formation of disinfection byproducts, including trihalomethanes (THMs). However, few epidemiologic studies have explored associations between THM exposure and mortality. This study included 6720 adults aged ≥40 years from the National Health and Nutrition Examination Survey 1999-2012 who had blood THM concentrations quantified. A higher risk of all-cause mortality was found across increasing quartile concentrations of blood chloroform (TCM) and total THMs (TTHMs; sum of all four THMs) (both p for trend = 0.02). Adults in the highest quartile of TCM and TTHM concentrations had hazard ratios (HRs) of 1.35 (95% confidence intervals 1.05-1.74) and 1.37 (1.05-1.79), respectively, for all-cause mortality, compared with adults in the lowest quartile. When cause-specific mortality was evaluated, a positive relationship was found between blood bromodichloromethane (BDCM), dibromochloromethane (DBCM), bromoform (TBM), total brominated THMs (Br-THMs; sum of BDCM, DBCM, and TBM), and TTHM concentrations and risk of cancer death and between blood TCM and TTHMs and risk of other cause (noncancer/nonheart disease) mortality. Our findings suggest that higher exposure to Br-THMs was associated with increased cancer mortality risk, whereas TCM was associated with a greater risk of noncancer/nonheart disease mortality.A series of octamethylcalix[4]pyrrole/ruthenium phosphinidene complexes (Na2[1=PR]) can be accessed by phosphinidene transfer from the corresponding RPA (A = C14H10, anthracene) compounds (R = tBu, iPr, OEt, NH2, NMe2, NEt2, NiPr2, NA, dimethylpiperidino). Isolation of the tert-butyl and dimethylamino derivatives allowed comparative studies of their 31P nuclear shielding tensors by magic-angle-spinning solid-state nuclear magnetic resonance spectroscopy. Density functional theory and natural chemical shielding analyses reveal the relationship between the 31P chemical shift tensor and the local ruthenium/phosphorus electronic structure. The general trend observed in the 31P isotropic chemical shifts for the ruthenium phosphinidene complexes was controlled by the degree of deshielding in the δ11 principal tensor component, which can be linked to the σRuP/πRuP* energy gap. A "δ22-δ33 crossover" effect for R = tBu was also observed, which was caused by different degrees of deshielding associated with polarizations of the σPR and σPR* natural bond orbitals.This paper describes the facile synthesis of haloaryl compounds with long-chain alkanoyl substituents by the destannylative acylation of haloaryls bearing tri-n-butyltin (Bu3Sn) substituents. The method allows the synthesis of many important synthons for novel functional materials in a highly efficient manner. The halo-tri-n-butyltin benzenes are obtained by the lithium-halogen exchange of commercially available bis-haloarenes and the subsequent reaction with Bu3SnCl. Under typical Friedel-Crafts conditions, i.e., the presence of an acid chloride and AlCl3, the haloaryls are acylated through destannylation. The reactions proceed fast ( less then 5 min) at low temperatures and thus are compatible with aromatic halogen substituents. Furthermore, the method is applicable to para-, meta-, and ortho-substitution and larger systems, as demonstrated for biphenyls. The generated tin byproducts were efficiently removed by trapping with silica/KF filtration, and most long-chain haloaryls were obtained chromatography-free. Molecular structures of several products were determined by X-ray single-crystal diffraction, and the crystal packing was investigated by mapping Hirshfeld surfaces onto individual molecules. A feasible reaction mechanism for the destannylative acylation reaction is proposed and supported through density functional theory (DFT) calculations. DFT results in combination with NMR-scale control experiments unambiguously demonstrate the importance of the tin substituent as a leaving group, which enables the acylation.Copper-exchanged zeolites have demonstrated high selectivity in methane-to-methanol conversion carried out on copper-oxo centers. Nevertheless, the reaction can only occur if the methane molecules reach the active site while the methanol molecules must leave the material without high energetic cost for the migration. In this context, we have used force field-based molecular dynamics simulations with the potential of mean force method to estimate the energy barrier in cage to cage diffusion of methane and methanol molecules in the chabazite framework type zeolite. The results show considerably higher energy barrier for methanol diffusion. The steric effect of the active site and the electrostatic environment favors the CH3OH diffusion toward nonactive cages where it tends to accumulate due to the strong interactions with the zeolite. The same behavior is observed in the water molecules distribution, which emphasizes the control of the electrostatic potential over the polar molecules migration. L-Arginine concentration For high concentration of polar molecules, the electrostatic effect is shielded and the driving force is reduced for CH3OH diffusion.