Search results for "Electronic Structure"
showing 10 items of 722 documents
A Molecular Electron Density Theory Study of the Reactivity of Azomethine Imine in [3+2] Cycloaddition Reactions
2017
The electronic structure and the participation of the simplest azomethine imine (AI) in [3+2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using DFT calculations at the MPWB1K/6-311G(d) level. Electron localisation function (ELF) topological analysis reveals that AI has a pseudoradical structure, while the conceptual DFT reactivity indices characterise this TAC as a moderate electrophile and a good nucleophile. The non-polar 32CA reaction of AI with ethylene takes place through a one-step mechanism with low activation energy, 5.3 kcal/mol-1. A bonding evolution theory (BET) study indicates that this reaction takes place through a non-…
Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene
1993
A newly proposed quantum chemical approach for ab initio calculations of electronic spectra of molecular systems is applied to the molecules ethene, trans‐1,3‐butadiene, and trans‐trans‐1,3,5‐hexatriene. The method has the aim of being accurate to better than 0.5 eV for excitation energies and is expected to provide structural and physical data for the excited states with good reliability. The approach is based on the complete active space (CAS) SCF method, which gives a proper description of the major features in the electronic structure of the excited state, independent of its complexity, accounts for all near degeneracy effects, and includes full orbital relaxation. Remaining dynamic ele…
First-principles electronic structure of spinelLiCr2O4:A possible half-metal
2004
We have employed first-principles electronic structure calculations to examine the hypothetical (but plausible) oxide spinel, ${\mathrm{LiCr}}_{2}{\mathrm{O}}_{4}$ with the ${d}^{2.5}$ electronic configuration. The cell (cubic) and internal (oxygen position) structural parameters have been obtained for this compound through structural relaxation in the first-principles framework. Within the one-electron band picture, we find that ${\mathrm{LiCr}}_{2}{\mathrm{O}}_{4}$ is magnetic, and a candidate half-metal. The electronic structure is substantially different from the closely related and well-known rutile half-metal ${\mathrm{CrO}}_{2}.$ In particular, we find a smaller conduction-band width…
Electronic Structure
2015
Abstract This chapter discusses the origin of fermionic shell structure in confined quantum systems, its application to metal clusters and clusters that are stabilized by an organic ligand layer (the so-called monolayer-protected clusters, MPCs). It reviews briefly the so-called superatom concept which has become central in the MPC field in recent years. It also contains a rather extensive table listing most of the structurally known MPCs, where the metal core is of gold, silver, copper, aluminum, or other main-group elements.
Atomic and electronic structure of the corundum (0001) surface: comparison with surface spectroscopies
1997
Abstract The electronic structure and geometry of the Al-terminated corundum (0001) surface were studied using a slab model within the ab-initio Hartree-Fock technique. The distance between the top Al plane and the next O basal plane is found to be considerably reduced on relaxation (by 0.57 A, i.e. by 68% of the corresponding interlayer distance in the bulk). An interpretation of experimental photoelectron spectra (UPS He I) and metastable impact electron spectra (MIES) is given using the calculated total density of states of the slab and the projections to the atoms, atomic orbitals, and He 1s floating atomic orbital at different positions above the surface. Calculated projected densities…
Revealing Charge-Transfer Dynamics at Electrified Sulfur Cathodes Using Constrained Density Functional Theory
2021
To understand and control the behavior of electrochemical systems, including batteries and electrocatalysts, we seek molecular-level details of the charge transfer mechanisms at electrified interfaces. Recognizing some key limitations of standard equilibrium electronic structure methods to model materials and their interfaces, we propose applying charge constraints to effectively separate electronic and nuclear degrees of freedom, which are especially beneficial to the study of conversion electrodes, where electronic charge carriers are converted to much slower polarons within a material that is nonmetallic. We demonstrate the need for such an approach within the context of sulfur cathodes …
Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes.
2014
A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported b…
Hybrid DFT calculations of the atomic and electronic structure for ABO3 perovskite (001) surfaces
2005
Abstract We present the results of first-principles calculations on two possible terminations of the (0 0 1) surfaces of SrTiO3, BaTiO3, and PbTiO3 perovskite crystals. Atomic structure and the electronic configurations were calculated for different 2D slabs, both stoichiometric and non-stoichiometric, using hybrid (B3PW) exchange-correlation technique and re-optimized basis sets of atomic (Gaussian) orbitals. Results are compared with previous calculations and available experimental data. The electronic density distribution near the surface and covalency effects are discussed in details for all three perovskites. Both SrTiO3 and BaTiO3 (0 0 1) surfaces demonstrate reduction of the optical …
Electronic Structures and Molecular Properties of Chalcogen Nitrides Se2N2 and SeSN2
2006
The electronic structures and molecular properties of S2N2 as well as the currently unknown chalcogen nitrides Se2N2 and SeSN2 have been studied using various ab initio and density functional methods. All molecules share a qualitatively similar electronic structure and can be primarily described as 2π-electron aromatics having minor singlet diradical character of 6−8% that can be attributed solely to the nitrogen atoms. This diradical character is manifested in the prediction of their molecular properties, in which coupled cluster and multiconfigurational approaches, as well as density functional methods, show the best performance. The conventional ab initio methods RHF and MP2 completely f…
Optical properties of wurtzite GaN/AlN quantum dots grown on non-polar planes: the effect of stacking faults in the reduction of the internal electri…
2016
The optical emission of non-polar GaN/AlN quantum dots has been investigated. The presence of stacking faults inside these quantum dots is evidenced in the dependence of the photoluminescence with temperature and excitation power. A theoretical model for the electronic structure and optical properties of non-polar quantum dots, taking into account their realistic shapes, is presented which predicts a substantial reduction of the internal electric field but a persisting quantum confined Stark effect, comparable to that of polar GaN/AlN quantum dots. Modeling the effect of a 3 monolayer stacking fault inside the quantum dot, which acts as zinc-blende inclusion into the wurtzite matrix, result…