Evolution Of Binding Energy Research Articles

Cooperative nature of the sulfur centered hydrogen bond: investigation of (H2S)n (n = 2-4) clusters using an affordable yet accurate level of theory.

Existing studies have shown that appreciably high level quantum chemical calculations are required to reproduce experimental energetic and geometric features of a H2S dimer. This condition severely restricts any practical possibility of obtaining reliable results for higher order H2S clusters. We have shown here that the binding energies calculated at the CCSD(T)/CBS level with counterpoise corrected geometries calculated at the MP2/aug-cc-pV(Q+d)Z level of theory excellently match with the experimental results for the H2S dimer. Subsequently, the above mentioned levels of theory were used for trimers and tetramers. (H2S)n (n = 2-4) clusters were found to show cooperative strengthening of S-HS hydrogen bonds, which is clearly evident from the evolution of binding energies and hydrogen bond lengths, with increasing cluster size. Localized molecular orbital energy decomposition analyses have been carried out to understand how the contributions of various energy components modulate with the size of the clusters and what are their relative contributions towards the overall stabilization of the clusters. Natural bond orbital and atoms in molecules analyses were also carried out in order to look into the evolution of the electronic charge transfer and electron density topology with cluster size.

Thermodynamic and kinetic properties of intrinsic defects and Mg transmutants in 3C–SiC determined by density functional theory

Density functional theory (DFT) is used to calculate the thermodynamic and kinetic properties of transmutant Mg in 3C–SiC due to high-energy neutron irradiation associated with the fusion nuclear environment. The formation and binding energies of intrinsic defects, Mg-related defects, and clusters in 3C–SiC are systematically calculated. The minimum energy paths and activation energies during point defect migration and small cluster evolution are studied using a generalized solid-state nudged elastic band (G-SSNEB) method with DFT energy calculations. Stable defect structures and possible defect migration mechanisms are identified. The evolution of binding energies during Mg2Si formation demonstrates that the formation of Mg2Si needs to overcome a critical nucleus size and nucleation barrier. It is found that C vacancies promote the formation of the Mg2Si nucleus, and formation of which results in a compressive stress field around the nucleus. These data are important inputs in meso- and macro-scale modeling and experiments to understand and predict the impact of Mg on phase stability, microstructure evolution, and performance of SiC and SiC-based materials during long-term neutron exposures.