Unconventional order/disorder behaviour in Al–Co–Cu–Fe–Ni multi-principal element alloys after casting and annealing

The effect of Cu concentration on the order/disorder behaviour of the AlCoCuxFeNi (x = 0.6 to 3.0) multi-principal element alloys was investigated. BCC and/or FCC phases were observed in the microstructures of the alloys after casting and annealing at 1050 ◦C followed by slow cooling. Interesting is that the alloys form ordered structures after casting and disordered structures after annealing and slow cooling, while the opposite would be expected. The ordering in the as-cast state is explained by the strong affinity of Al to transition metals, which results in the formation of supercell structures having sublattices occupied by certain elements only. Disordering after annealing has two reasons. Either the phase is composed of nearly pure element (Cu) and is disordered by default or it is composed of randomly distributed nano-segregated regions within a single phase resulting in a uniform distribution of all elements in the sublattices and therefore appearing to be macroscopically disordered. The reason for the formation of such nano-segregated areas might reside in the reduction of Gibbs free energy due to the annealing by the interplay between enthalpy and entropy

NMR absolute shielding scale and nuclear magnetic dipole moment of 207 Pb

An absolute shielding scale is proposed for 207Pb nuclear magnetic resonance (NMR) spectroscopy. It is based on ab initio calculations performed on an isolated tetramethyllead Pb(CH3)4 molecule and the assignment of the experimental resonance frequency from the gas-phase NMR spectra of Pb(CH3)4, extrapolated to zero density of the buffer gas to obtain the result for an isolated molecule. The computed207Pb shielding constant is 10 790 ppm for the isolated molecule, leading to a shielding of 10799.7 ppm for liquid Pb(CH3)4 which is the accepted reference standard for 207Pb NMR spectra. The new experimental and theoretical data are used to determine μ(207Pb), the nuclear magnetic dipole moment of 207Pb, by applying the standard relationship between NMR frequencies, shielding constants and nuclear moments of two nuclei in the same external magnetic field. Using the gas-phase 207Pb and (reference) proton results and the theoretical value of the Pb shielding in Pb(CH3)4, we find μ(207Pb) = 0.59064 μN. The analysis of new experimental and theoretical data obtained for the Pb2+ ion in water solutions provides similar values of μ(207Pb), in the range of 0.59000–0.59131 μN

Indirect NMR spin-spin coupling constants in diatomic alkali halides

We report the Nuclear Magnetic Resonance (NMR) spin–spin coupling constants for diatomic alkali halides MX, where M = Li, Na, K, Rb, or Cs and X = F, Cl, Br, or I. The coupling constants are determined by supplementing the non-relativistic coupled-cluster singles-and-doubles (CCSD) values with relativistic corrections evaluated at the four-component density-functional theory (DFT) level. These corrections are calculated as the differences between relativistic and non-relativistic values determined using the PBE0 functional with 50% exact-exchange admixture. The total coupling constants obtained in this approach are in much better agreement with experiment than the standard relativistic DFT values with 25% exact-exchange, and are also noticeably better than the relativistic PBE0 results obtained with 50% exact-exchange. Further improvement is achieved by adding rovibrational corrections, estimated using literature data