RESUMEN

The structural evolution of black arsenic-phosphorous (b-AsxP1-x) alloys with varying arsenic concentrations was investigated under hydrostatic pressure usingin situRaman spectroscopy. High-pressure experiments were conducted using a diamond anvil cell, which revealed pressure-induced shifts in vibrational modes associated with P-P bonds (A1g,A2g,B2g), As-As bonds (A1g,A2g,B2g), and As-P bonds in b-AsxP1-xalloys. Two distinct pressure regimes were observed. In the first regime (region I), all vibrational modes exhibited a monotonic upshift, indicating phonon hardening due to hydrostatic pressure. In the second regime (region II), As0.4P0.6and As0.6P0.4alloys displayed a linear blueshift (or negligible change in some modes) at a reduced rate, suggesting local structural reorganization with less compression on the bonds. Notably, the alloy with the highest As concentration, As0.8P0.2, exhibited anomalous behavior in the second pressure regime, with a downward shift observed in all As-As and As-P Raman modes (and some P-P modes). Interestingly, the emergence of new peaks corresponding to theEgmode andA1gmode of the gray-As phase was observed in this pressure range, indicating compressive strain-induced structural changes. The anomalous change in region II confirms the formation of a new local structure, characterized by elongation of the P-P, As-As, and As-P bonds along the zigzag direction within the b-AsxP1-xphase, possibly near the grain boundary. Additionally, a gray-As phase undergoes compressive structural changes. This study underscores the significance of pressure in inducing structural transformations and exploring novel phases in two-dimensional materials, including b-AsxP1-xalloys.

RESUMEN

Subsystem density functional theory (DFT) is emerging as a powerful electronic structure method for large-scale simulations of molecular condensed phases and interfaces. Key to its computational efficiency is the use of approximate nonadditive noninteracting kinetic energy functionals. Unfortunately, currently available nonadditive functionals lead to inaccurate results when the subsystems interact strongly such as when they engage in chemical reactions. This work disrupts the status quo by devising a workflow that extends subsystem DFT's applicability also to strongly interacting subsystems. This is achieved by implementing a fully automated adaptive definition of subsystems which is realized during geometry optimizations or ab initio molecular dynamics simulations. The new method prescribes subsystem merging and splitting events redistributing the resources (both for work and data) in an efficient way making use of modern parallelization strategies and object-oriented programming. We showcase the method with examples probing from moderate-to-strong inter-subsystem interactions, opening the door to using subsystem DFT for modeling chemical reactions in molecular condensed phases with a black box computational tool.

Asunto(s)

RESUMEN

The process of hydrazine gas adsorption on layered WS2 has been systematically studied from first principle calculations. Our results demonstrate that this adsorption process is exothermic, and hydrazine molecules are physically adsorbed. The layer-dependent adsorption energy and interlayer separation induced by van der Waals interaction exerted by hydrazine molecules lead to the difficulty in desorbing hydrazine molecules from layered WS2 as the number of layers increases. The most interesting finding is the emergence of localized impurity states below the Fermi level upon the hydrazine adsorption, irrespective of the number of WS2 layers, resulting in a significant effect on the band structures and subsequently changing its electrical conductivity. Furthermore, a layer-dependent small charge transfer occurs between hydrazine and layered WS2, leading to a charge redistribution and considerable polarization in the adsorbed systems. The existence of defects and the humidity, on the other hand, influences the sensitivity of layered WS2 to the hydrazine adsorption. Obtained results show that a perfectly layered WS2 might be a promising candidate as an efficient nanosensor to detect such toxic gas in dry environment.