Search results for "quantum chemistry"
showing 10 items of 632 documents
Comparative theoretical study of the Ag–MgO (100) and (110) interfaces
1999
We have calculated the atomic and electronic structures of Ag–MgO(100) and (110) interfaces using a periodic (slab) model and an ab initio Hartree–Fock approach with a posteriori electron correlation corrections. The electronic structure information includes interatomic bond populations, effective charges, and multipole moments of ions. This information is analyzed in conjunction with the interface binding energy and the equilibrium distances for both interfaces for various coverages. There are significant differences between partly covered surfaces and surfaces with several layers of metal, and these can be understood in terms of electrostatics and the electron density changes. For complet…
First principles hybrid Hartree-Fock-DFT calculations of bulk and (001) surface F centers in oxide perovskites and alkaline-earth fluorides
2020
Valuable discussions with E. A. Kotomin are gratefully acknowledged. Research contribution of R. E. and A. I. P. has been performed within the framework of the EUROfusion Enabling Research project: ENR-MFE19.ISSP-UL-02 “Advanced experimental and theoretical analysis of defect evolution and structural disordering in optical and dielectric materials for fusion applications.” The views and opinions expressed herein do not necessarily reflect those of the European Commission.
Ab initio calculations of CaZrO3, BaZrO3, PbTiO3 and SrTiO3 (001), (011) and (111) surfaces as well as their (001) interfaces
2019
We carried out ab initio calculations for technologically important ABO3 perovskites, like, CaZrO3, BaZrO3, PbTiO3 and SrTiO3, their (001), (011) and (111) surfaces as well as (001) interfaces. For...
Interaction of carbon with microstructural defects in a W-Re matrix: An ab initio assessment
2019
The interaction of carbon atoms with point defects and the core of edge and screw dislocations with Burgers vector a 0 / 2 ⟨ 111 ⟩ in W and a W-Re matrix is studied by means of ab initio calculations. The structure and energetics of the ground-state atomic configurations are presented and rationalized. It is found that di-vacancies, which are thermally unstable in pure W according to the state-of-the-art ab initio calculations, can nucleate at C and Re-C complexes, which fill the gap in the explanation of the emergence of nanovoids observed experimentally under irradiation. Also, on the basis of the recent experimental evidence and our calculations, the temperature ranges for the manifestat…
Ab initio calculations of the electronic structure for Mn2+-doped YAlO3 crystals
2020
The electronic structure of Mn2+ ion substituted for the host Y atom in orthorhombic bulk YAlO3 crystals has been calculated by means of hybrid exchange-correlation functional HSE within density functional theory. The supercell approach has been used to simulate in Pbnm YAlO3 crystal the point defects, Mn-dopant and compensated the F+ center (oxygen vacancy with one trapped electron), to make unit cell neutral. Large 2 × 2 × 2 supercells of 160 atoms allow us to simulate substitutional point defect with concentration of about 3%. Mn2+ ions substituting for host Y form covalent Mn–O bonds, in opposite to the mostly ionic Y–O bond. The F center inserted to compensate the Mn2+ dopant in YAlO3 …
Ab initio calculations of structural, electronic and vibrational properties of BaTiO3 and SrTiO3 perovskite crystals with oxygen vacancies
2020
The first-principles (ab initio) computations of the structural, electronic, and phonon properties have been performed for cubic and low-temperature tetragonal phases of BaTiO3 and SrTiO3 perovskite crystals, both stoichiometric and non-stoichiometric (with neutral oxygen vacancies). Calculations were performed with the CRYSTAL17 computer code within the linear combination of atomic orbitals approximation, using the B1WC advanced hybrid exchange-correlation functional of the density-functional-theory (DFT) and the periodic supercell approach. Various possible spin states of the defective systems were considered by means of unrestricted (open shell) DFT calculations. It was demonstrated that…
Study of the thermochromic phase transition in CuMo1−xWxO4 solid solutions at the W L3-edge by resonant X-ray emission spectroscopy
2021
Abstract Polycrystalline CuMo 1 − x W x O 4 solid solutions were studied by resonant X-ray emission spectroscopy (RXES) at the W L 3 -edge to follow a variation of the tungsten local atomic and electronic structures across thermochromic phase transition as a function of sample composition and temperature. The experimental results were interpreted using ab initio calculations. The crystal-field splitting parameter Δ for the 5d(W)-states was obtained from the analysis of the RXES plane and was used to evaluate the coordination of tungsten atoms. Temperature-dependent RXES measurements were successfully employed to determine the hysteretic behaviour of the structural phase transition between t…
On the ‘expanded local mode’ approach applied to the methane molecule: isotopic substitution CH2D2←CH4
2011
On the basis of a compilation of the ‘expanded local mode’ model and the general isotopic substitution theory, sets of simple analytical relations between different spectroscopic parameters (harmonic frequencies, ωλ, anharmonic coefficients, x λμ, ro-vibrational coefficients, , different kinds of Fermi- and Coriolis-type interaction parameters) of the CH2D2 molecule are derived. All of them are expressed as simple functions of a few initial spectroscopic parameters of the mother, CH4, molecule. Test calculations with the derived isotopic relations show that, in spite of a total absence of initial information about the CH2D2 species, the numerical results of the calculations have a very good…
Towards highly accurate ab initio thermochemistry of larger systems: benzene.
2011
The high accuracy extrapolated ab initio thermochemistry (HEAT) protocol is applied to compute the total atomization energy (TAE) and the heat of formation of benzene. Large-scale coupled-cluster calculations with more than 1500 basis functions and 42 correlated electrons as well as zero-point energies based on full cubic and (semi)diagonal quartic force fields obtained with the coupled-cluster singles and doubles with perturbative treatment of the triples method and atomic natural orbital (ANO) triple- and quadruple-zeta basis sets are presented. The performance of modifications to the HEAT scheme and the scaling properties of its contributions with respect to the system size are investiga…
A QM/MM Approach Using the AMOEBA Polarizable Embedding: From Ground State Energies to Electronic Excitations
2016
International audience; A fully polarizable implementation of the hybrid Quantum Mechanics/Molecular Mechanics approach is presented, where the classical environment is described through the AMOEBA polarizable force field. A variational formalism, offering a self-consistent 1 relaxation of both the MM induced dipoles and the QM electronic density is used for ground state energies and extended to electronic excitations in the framework of Time-Dependent Density Functional Theory combined with a state specific response of the classical part. An application to the calculation of the solvatochromism of the pyridinium N-phenolate betaine dye used to define the solvent ET30 scale is presented. Th…