Search results for "ab-initio"
showing 10 items of 34 documents
First principles simulation of amorphous InSb
2013
Ab initio molecular dynamics simulations based on density functional theory have been performed to generate a model of amorphous InSb by quenching from the melt. The resulting network is mostly tetrahedral with a minor fraction ($10%$) of atoms in a fivefold coordination. The structural properties are in good agreement with available x-ray diffraction and extended x-ray-absorption fine structure data and confirm the proposed presence of a sizable fraction of homopolar In-In and Sb-Sb bonds whose concentration in our model amounts to about $20%$ of the total number of bonds.
Trace element fractionation through halite crystallisation: Geochemical mechanisms and environmental implications
2019
Halite is an important mineral for industry, agriculture and food production. It crystallises after water evaporation, while the progressive growth of dissolved metal ions in brines is occurring. Then, halite exploitation may provide the delivery of metal ions in the environment and the mechanism of this trace element accumulation should be studied. In this work we investigate the distribution of lanthanides and Y (hereafter named Rare Earth Elements, REE), Zr and Hf between crystallising halite and brines in the Dead Sea as geochemical tools for recognising the mechanism of metal ion removal from brines and accumulation in halite. Halite forms cubic crystals where octahedral planes sometim…
Electronic and magnetic properties of VOCl/FeOCl antiferromagnetic heterobilayers
2021
We study the electronic properties of the heterobilayer of vanadium and iron oxychlorides, VOCl and FeOCl, two layered air stable van der Waals insulating oxides with different types of antiferromagnetic order in bulk: VOCl monolayers are ferromagnetic (FM) whereas the FeOCl monolayers are antiferromagnetic (AF). We use density functional theory (DFT) calculations, with Hubbard correction that is found to be needed to describe correctly the insulating nature of these compounds. We compute the magnetic anisotropy and propose a spin model Hamiltonian. Our calculations show that interlayer coupling in weak and ferromagnetic so that magnetic order of the monolayers is preserved in the heterobil…
Ultra-broad spectral photo-response in FePS3 air-stable devices
2021
Van der Waals materials with narrow energy gaps and efficient response over a broadband optical spectral range are key to widen the energy window of nanoscale optoelectronic devices. Here, we characterize FePS as an appealing narrow-gap p-type semiconductor with an efficient broadband photo-response, a high refractive index, and a remarkable resilience against air and light exposure. To enable fast prototyping, we provide a straightforward guideline to determine the thickness of few-layered FePS nanosheets extracted from the optical transmission characteristics of several flakes. The analysis of the electrical photo-response of FePS devices as a function of the excitation energy confirms a …
The electronic structure of zircon-type orthovanadates: Effects of high-pressure and cation substitution
2012
The electronic structure of four ternary-metal oxides containing isolated vanadate ions is studied. Zircon-type YVO4, YbVO4, LuVO4, and NdVO4 are investigated by high-pressure optical-absorption measurements up to 20 GPa. First-principles calculations based on density-functional theory were also performed to analyze the electronic band structure as a function of pressure. The electronic structure near the Fermi level originates largely from molecular orbitals of the vanadate ion, but cation substitution influence these electronic states. The studied ortovanadates, with the exception of NdVO4, undergo a zircon-scheelite structural phase transition that causes a collapse of the band-gap energ…
Molecular dynamics of CH4/N2 mixtures on a flexible graphene layer: adsorption and selectivity case study
2019
We theoretically investigate graphene layers, proposing them as membranes of subnanometer size suitable for CH4/N2 separation and gas uptake. The observed potential energy surfaces, representing the intermolecular interactions within the CH4/N2 gaseous mixtures and between these and the graphene layers, have been formulated by adopting the so-called Improved Lennard-Jones (ILJ) potential, which is far more accurate than the traditional Lennard-Jones potential. Previously derived ILJ force fields are used to perform extensive molecular dynamics simulations on graphene's ability to separate and adsorb the CH4/N2 mixture. Furthermore, the intramolecular interactions within graphene were explic…
Multiple Decay Mechanisms and 2D-UV Spectroscopic Fingerprints of Singlet Excited Solvated Adenine-Uracil Monophosphate
2016
The decay channels of singlet excited adenine uracil monophosphate (ApU) in water are studied with CASPT2//CASSCF:MM potential energy calculations and simulation of the 2D-UV spectroscopic fingerprints with the aim of elucidating the role of the different electronic states of the stacked conformer in the excited state dynamics. The adenine 1La state can decay without a barrier to a conical intersection with the ground state. In contrast, the adenine 1Lb and uracil S(U) states have minima that are separated from the intersections by sizeable barriers. Depending on the backbone conformation, the CT state can undergo inter-base hydrogen transfer and decay to the ground state through a conical …
Electromagnetic moments of scandium isotopes and $N=28$ isotones in the distinctive $0f_{7/2}$ orbit
2022
The electric quadrupole moment of $^{49}$Sc was measured by collinear laser spectroscopy at CERN-ISOLDE to be $Q_{\rm s}=-0.159(8)$ $e$b, and a nearly tenfold improvement in precision was reached for the electromagnetic moments of $^{47,49}$Sc. The single-particle behavior and nucleon-nucleon correlations are investigated with the electromagnetic moments of $Z=21$ isotopes and $N=28$ isotones as valence neutrons and protons fill the distinctive $0f_{7/2}$ orbit, respectively, located between magic numbers, 20 and 28. The experimental data are interpreted with shell-model calculations using an effective interaction, and ab-initio valence-space in-medium similarity renormalization group calcu…
Cation Environment of BaCeO3−Based Protonic Conductors II: New Computational Models
2011
Quantum chemical calculations have been carried out to simulate Y-doped BaCeO(3) derivatives. Hartree-Fock energy functional was used to study octahedral site environments embedded in a Pmcn orthorhombic framework, showing local arrangement characterized by Ce-O-Ce, Ce-O-Y, and Y-O-Y (Z-O-Ξ) configurations and including or not hydrogen close to the moieties encompassing those configurations. The latter are, in fact, representative of - and, in our modeling approach, were treated as - local arrangements that could be found in Y:BaCeO(3)-doped materials. The geometrical optimizations performed on the structural models and a detailed orbital analysis of these systems allowed us to confirm and …
Experimental and theoretical study on the optical properties of LaVO4 crystals under pressure
2018
We report optical absorption and luminescence measurements in pure and trivalent neodymium (Nd3+) doped LaVO4 crystals up to 25 GPa. Nd3+ luminescence has been employed as a tool to follow the structural changes in the crystal. We also present band-structure and crystal-field calculations that provide the theoretical framework to accurately explain the observed experimental results. In particular, both optical absorption and luminescence measurements evidence that a phase transition takes place close to 12 GPa. They also provide information on the pressure dependence of the band-gap as well as the emission lines under compression. We found drastic changes in the optical properties of LaVO4 …