Search results for "Ab initio (calculations)"
showing 10 items of 62 documents
Two C3-symmetric Dy3 III complexes with triple di-μ-methoxo-μ-phenoxo bridges, magnetic ground state, and single-molecule magnetic behavior
2014
Two series of isostructural C3-symmetric Ln3 complexes Ln3·[BPh4] and Ln3·0. 33[Ln(NO3)6] (in which LnIII=Gd and Dy) have been prepared from an amino-bis(phenol) ligand. X-ray studies reveal that LnIII ions are connected by one μ2-phenoxo and two μ3-methoxo bridges, thus leading to a hexagonal bipyramidal Ln3O5 bridging core in which LnIII ions exhibit a biaugmented trigonal-prismatic geometry. Magnetic susceptibility studies and ab initio complete active space self-consistent field (CASSCF) calculations indicate that the magnetic coupling between the DyIII ions, which possess a high axial anisotropy in the ground state, is very weakly antiferromagnetic and mainly dipolar in nature. To redu…
Ab initio calculations of the atomic and electronic structure of MgF2 (011) and (111) surfaces
2011
Abstract The results of ab initio slab calculations of surface relaxations, rumplings and charge distribution for the different terminations of the MgF2 (011) and (111) polar surfaces are presented and discussed. We have employed the computer code CRYSTAL with the Gaussian basis set and the hybrid B3PW exchange-correlation functional. Despite the ionic nature of the chemical bonding at both surfaces, a considerable decrease of the optical band gap is predicted (1.3 eV or 10%) for the (111) surface as compared to the bulk.
Structural and Vibrational Properties of Corundum-type In2O3 Nanocrystals under Compression
2017
[EN] This work reports the structural and vibrational properties of nanocrystals of corundum-type In2O3 (rh-In2O3) at high pressures by using angle-dispersive x-ray diffraction and Raman scattering measurements up to 30 GPa. The equation of state and the pressure dependence of the Raman-active modes of the corundum phase in nanocrystals are in good agreement with previous studies on bulk material and theoretical simulations on bulk rh-In2O3. Nanocrystalline rh-In2O3 showed stability under compression at least up to 20 GPa, unlike bulk rh-In2O3 which gradually transforms to the orthorhombic Pbca (Rh2O3-III-type) structure above 12 14 GPa. The different stability range found in nanocrystallin…
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…
Solid-state NMR and computational investigation of solvent molecule arrangement and dynamics in isostructural solvates of droperidol.
2015
(13)C, (15)N and (2)H solid-state NMR spectroscopy have been used to rationalize arrangement and dynamics of solvent molecules in a set of isostructural solvates of droperidol. The solvent molecules are determined to be dynamically disordered in the methanol and ethanol solvates, while they are ordered in the acetonitrile and nitromethane solvates. (2)H NMR spectra of deuterium-labelled samples allowed the characterization of the solvent molecule dynamics in the alcohol solvates and the non-stoichiometric hydrate. The likely motion of the alcohol molecules is rapid libration within a site, plus occasional exchange into an equivalent site related by the inversion symmetry, while the water mo…
Pressure effects on the vibrational properties of alpha-Bi2O3: an experimental and theoretical study
2014
We report an experimental and theoretical high-pressure study of the vibrational properties of synthetic monoclinic bismuth oxide (alpha-Bi2O3), also known as mineral bismite. The comparison of Raman scattering measurements and theoretical lattice-dynamics ab initio calculations is key to understanding the complex vibrational properties of bismite. On one hand, calculations help in the symmetry assignment of phonons and to discover the phonon interactions taking place in this low-symmetry compound, which shows considerable phonon anticrossings; and, on the other hand, measurements help to validate the accuracy of first-principles calculations relating to this compound. We have also studied …
The Molecular and Crystal Structure of tert-Butyl N.ALPHA.-tert-Butoxycarbonyl-L-(S-trityl)cysteinate and the Conformation-Stabilizing Function of We…
2001
The title compound, C31H37NO4S [systematic name: (R)-tert-butyl-2-[(tert-butoxycarbonyl)amino]-3-(tritylsulfanyl)propanoate] is an L-cysteine derivative with three functions: NH2, COOH and SH, blocked by protecting groups tert-butoxycarbonyl, tert-butyl and trityl, respectively. The main chain of the molecule adopts the extended, nearly all-trans C5 conformation with the intramolecular N-H...O=C hydrogen bond. The urethane group is not involved in any intermolecular hydrogen bonding. Only weak intermolecular hydrogen bonds and hydrophobic contacts are observed in the crystal structure. These are C-H...O hydrogen bonds and CH/pi interactions with donor...acceptor distances, C...O ca. 3.5 A a…
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 …
Synthesis and characterization of indium oxide at high pressures
2018
Introducción: La naturaleza es sorprendente pero a la vez limitada. A mi entender, nada tiene más potencial que aplicar el ingenio humano para modificar lo que nos rodea y crear algo completamente nuevo. La Física de la Materia Condensada es un campo que actualmente está ganando importancia en la Física moderna. En virtud de los éxitos logrados en Física de la Materia Condensada se han producido enormes avances en el campo de la electrónica cuántica, de los semiconductores y de la ciencia de materiales, teniendo como resultado numerosas aplicaciones tecnológicas que han cambiado nuestras vidas drásticamente en los últimos 50 años. Una de las ramas de la Física de la Materia Condensada es el…
Radiation effects on silica-based preforms and optical fibers-II: Coupling ab initio simulations and experiments
2008
International audience; Abstract—Experimental characterization through electron paramagnetic resonance (EPR) and confocal luminescence microscopy (CML) of a Ge-doped glass (preform and fiber) reveals the generation of several point defects by 10 keV X-ray radiation-induced attenuation: GeE', Ge(1), Ge(2), and Ge-ODC. The generation mechanisms of Ge-ODC and charged defects like GeE' centers are studied through ab initio simulation. Our calculations used a 108 atom supercell with a glass composition comparable to the Ge-doped core or to the pure-silica cladding of the canonical sample. The large size of our cell allows us to study the influence of the local environment surrounding the X-ODC d…