Structural Isomeric Effect on Spin Transport in Molecular Semiconductors.

Molecular semiconductor (MSC) is a promising candidate for spintronic applications benefiting from its long spin lifetime caused by light elemental-composition essence and thus weak spin-orbit coupling (SOC). According to current knowledge, the SOC effect, normally dominated by the elemental composition, is the main spin-relaxation causation in MSCs, and thus the molecular structure-induced SOC change is one of the most concerned issues. In theoretical study, molecular isomerism, a most prototype phenomenon, has long been considered to possess little difference on spin transport previously, since elemental compositions of isomers are totally the same. However, here in this study, quite different spin-transport performances are demonstrated in ITIC and its structural isomers BDTIC experimentally, for the first time, though the charge transport and molecular stacking of the two films are very similar. By further experiments of electron-paramagnetic resonance and density-functional-theory calculations, it is revealed that noncovalent-conformational locks (NCLs) formed in BDTIC can lead to enhancement of SOC and thus decrease the spin lifetime. Hence, this study suggests the influences from the structural-isomeric effect must be considered for developing highly efficient spin-transport MSCs, which also provides a reliable theoretical basis for solving the great challenge of quantificational measurement of NCLs in films in the future.

Machine Learning-Accelerated Discovery of A2BC2 Ternary Electrides with Diverse Anionic Electron Densities.

This study combines machine learning (ML) and high-throughput calculations to uncover new ternary electrides in the A2BC2 family of compounds with the P4/mbm space group. Starting from a library of 214 known A2BC2 phases, density functional theory calculations were used to compute the maximum value of the electron localization function, indicating that 42 are potential electrides. A model was then trained on this data set and used to predict the electride behavior of 14,437 hypothetical compounds generated by structural prototyping. Then, the stability and electride features of the 1254 electride candidates predicted by the model were carefully checked by high-throughput calculations. Through this tiered approach, 41 stable and 104 metastable new A2BC2 electrides were predicted. Interestingly, all three kinds of electrides, i.e., electron-deficient, electron-neutral, and electron-rich electrides, are present in the set of predicted compounds. Three of the most promising new electrides (two electron-rich, Nd2ScSi2 and La2YbGe2, and one electron-deficient Y2LiSi2) were then successfully synthesized and characterized experimentally. Furthermore, the synthesized electrides were found to exhibit high catalytic activities for NH3 synthesis under mild conditions when Ru-loaded. The electron-deficient Y2LiSi2, in particular, was seen to exhibit a good balance of catalytic activity and chemical stability, suggesting its future application in catalysis.