Search results for "Calculation"
showing 10 items of 594 documents
Comparison of different theory models and basis sets in the calculation of 13C NMR chemical shifts of natural products.
2004
The influence of the calculation method in mimicking experimental 13C NMR chemical shifts of 15 low-polarity natural products singularly containing 10–20 carbon atoms was investigated by employing different quantum chemistry approaches and basis sets, both in the preliminary geometry optimizations and in the following single-point 13C GIAO calculations of the NMR chemical shifts. The geometries of the involved species were optimized at the PM3, HF, B3LYP and mPW1PW91 levels whereas the 13C NMR parameters were determined at the HF, B3LYP and mPW1PW91 levels. Different combinations of basis sets were also tested. The consistency and efficiency of the considered combinations of geometry optimi…
Four-Component Relativistic DFT Calculations of C-13 Chemical Shifts of Halogenated Natural Substances
2015
We have calculated the (13) C NMR chemical shifts of a large ensemble of halogenated organic molecules (81 molecules for a total of 250 experimental (13) C NMR data at four different levels of theory), ranging from small rigid organic compounds, used to benchmark the performance of various levels of theory, to natural substances of marine origin with conformational degrees of freedom. Carbon atoms bonded to heavy halogen atoms, particularly bromine and iodine, are known to be rather challenging when it comes to the prediction of their chemical shifts by quantum methods, due to relativistic effects. In this paper, we have applied the state-of-the-art four-component relativistic density funct…
A Catalyst Designed for the Enantioselective Construction of Methyl- and Alkyl-Substituted Tertiary Stereocenters
2015
Tertiary methyl-substituted stereocenters are present in numerous biologically active natural products. Reported herein is a catalytic enantioselective method for accessing these chiral building blocks using the Mukaiyama-Michael reaction between silyl ketene thioacetals and acrolein. To enable remote enantioface control on the nucleophile, a new iminium catalyst, optimized by three-parameter tuning and by identifying substituent effects on enantioselectivity, was designed. The catalytic process allows rapid access to chiral thioesters, amides, aldehydes, and ketones bearing an α-methyl stereocenter with excellent enantioselectivities, and allowed rapid access to the C4-C13 segment of (-)-b…
Inference of proto-neutron star properties from gravitational-wave data in core-collapse supernovae
2021
The eventual detection of gravitational waves from core-collapse supernovae (CCSN) will help improve our current understanding of the explosion mechanism of massive stars. The stochastic nature of the late post-bounce gravitational wave signal due to the non-linear dynamics of the matter involved and the large number of degrees of freedom of the phenomenon make the source parameter inference problem very challenging. In this paper we take a step towards that goal and present a parameter estimation approach which is based on the gravitational waves associated with oscillations of proto-neutron stars (PNS). Numerical simulations of CCSN have shown that buoyancy-driven g-modes are responsible …
Johnson-Nyquist Noise Effects in Neutron Electric-Dipole-Moment Experiments
2021
Magnetic Johnson-Nyquist noise (JNN) originating from metal electrodes, used to create a static electric field in neutron electric-dipole-moment (nEDM) experiments, may limit the sensitivity of measurements. We present here the first dedicated study on JNN applied to a large-scale long-measurement-time experiment with the implementation of a co-magnetometry. In this study, we derive surface- and volume-averaged root-mean-square normal noise amplitudes at a certain frequency bandwidth for a cylindrical geometry. In addition, we model the source of noise as a finite number of current dipoles and demonstrate a method to simulate temporal and three-dimensional spatial dependencies of JNN. The c…
Does Multi-Component Strategy Training Improve Calculation Fluency Among Poor Performing Elementary School Children?
2018
The aim of the present study was to extend the previous intervention research in math by examining whether elementary school children with poor calculation fluency benefit from strategy training focusing on derived fact strategies and following an integrative framework, i.e., integrating factual, conceptual, and procedural arithmetic knowledge. It was also examined what kind of changes can be found in frequency of using different strategies. A quasi-experimental design was applied, and the study was carried out within the context of the school and its schedules and resources. Twenty schools in Finland volunteered to participate, and 1376 children were screened in for calculation fluency pro…
Reaction of LiArMe6 (ArMe6ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2) with indium(I)chloride yields three m-terphenyl stabilized mixed-valent organoindium su…
2016
Indium(I)chloride reacts with LiArMe6 (ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2) in THF to give three new mixed-valent organoindium subhalides. While the 1:1 reaction of InCl with LiArMe6 yields the known metal-rich cluster In8(ArMe6)4 (1), the use of freshly prepared LiArMe6 led to incorporation of iodide, derived from the synthesis of LiArMe6, into the structures, to afford In4(ArMe6)4I2 (2) along with minor amounts of In3(ArMe6)3I2 (3). When the same reaction was performed in 4:3 stoichiometry, the mixed-halide compound In3(ArMe6)3ClI (4) was obtained. Further increasing the chloride:aryl ligand ratio resulted in the formation of the known mixed-halide species In4(ArMe6)4Cl2I2 that can also be…
Structure ofD-ribonic acid-dimethyltin(IV) in coordinating solvents: an experimental and DFT119Sn NMR study
2006
We have investigated a newly synthesized complex of D-ribonic acid with dimethyltin(IV). The structure of the complex in solution has been characterized by means of 1 H, 13 C, and 119 Sn NMR and by DFT calculations. The comparison of experimental and computational results allowed the determination of the stable conformation in solution as well as the detection of a dimerization process. Moreover, evidence is given of active coordination of the metal by the solvent.
Reactions of m-Terphenyl-Stabilized Germylene and Stannylene with Water and Methanol: Oxidative Addition versus Arene Elimination and Different React…
2015
Reactions of the divalent germylene Ge(ArMe6)2 (ArMe6 = C6H3-2,6-{C6H2-2,4,6-(CH3)3}2) with water or methanol gave the Ge(IV) insertion product (ArMe6)2Ge(H)OH (1) or (ArMe6)2Ge(H)OMe (2), respectively. In contrast, its stannylene congener Sn(ArMe6)2 reacted with water or methanol to produce the Sn(II) species {ArMe6Sn(μ-OH)}2 (3) or {ArMe6Sn(μ-OMe)}2 (4), respectively, with elimination of ArMe6H. Compounds 1–4 were characterized by IR and NMR spectroscopy as well as by X-ray crystallography. Density functional theory calculations yielded mechanistic insight into the formation of (ArMe6)2Ge(H)OH and {ArMe6Sn(μ-OH)}2. The insertion of an m-terphenyl-stabilized germylene into the O–H bond was…
Testing the nature of the Λ(1520)-resonance in proton-induced production
2006
The $\Lambda(1520)$ resonance has been recently studied in a unitarized coupled channel formalism with $\pi\Sigma(1385)$, $K\Xi(1530)$, $\bar{K}N$ and $\pi\Sigma$ as constituents blocks. We provide a theoretical study of the predictions of this model in physical observables of the $pp\to pK^+K^-p$ and $pp\to pK^+\pi^0\pi^0\Lambda$ reactions. In particular, we show that the ratio between the $\pi^0\pi^0\Lambda$ and $K^-p$ mass distributions can provide valuable information on the ratio of the couplings of the $\Lambda(1520)$ resonance to $\pi\Sigma(1385)$ and $\bar{K}N$ that the theory predicts. Calculations are done for energies which are accessible in an experimental facility like COSY at …