Topic
Atomic orbital
About: Atomic orbital is a research topic. Over the lifetime, 6994 publications have been published within this topic receiving 221887 citations.
Papers published on a yearly basis
1 / 2
Papers
TL;DR: In this paper, an analysis in quantitative form is given in terms of breakdowns of the electronic population into partial and total ''gross atomic populations'' and ''overlap populations'' for molecules.
Abstract: With increasing availability of good all‐electron LCAO MO (LCAO molecular orbital) wave functions for molecules, a systematic procedure for obtaining maximum insight from such data has become desirable. An analysis in quantitative form is given here in terms of breakdowns of the electronic population into partial and total ``gross atomic populations,'' or into partial and total ``net atomic populations'' together with ``overlap populations.'' ``Gross atomic populations'' distribute the electrons almost perfectly among the various AOs (atomic orbitals) of the various atoms in the molecule. From these numbers, a definite figure is obtained for the amount of promotion (e.g., from 2s to 2p) in each atom; and also for the gross charge Q on each atom if the bonds are polar. The total overlap population for any pair of atoms in a molecule is in general made up of positive and negative contributions. If the total overlap population between two atoms is positive, they are bonded; if negative, they are antibonded. Tables of gross atomic populations and overlap populations, also gross atomic charges Q, computed from SCF (self‐consistent field) LCAO‐MO data on CO and H2O, are given. The amount of s‐p promotion is found to be nearly the same for the O atom in CO and in H2O (0.14 electron in CO and 0.15e in H2O). For the C atom in CO it is 0.50e. For the N atom in N2 it is 0.26e according to calculations by Scherr. In spite of very strong polarity in the π bonds in CO, the σ and π overlap populations are very similar to those in N2. In CO the total overlap population for the π electrons is about twice that for the σ electrons. The most easily ionized electrons of CO are in an MO such that its gross atomic population is 94% localized on the carbon atom; these electrons account for the (weak) electron donor properties of CO. A comparison between changes of bond lengths observed on removal of an electron from one or another MO of CO and H2, and corresponding changes in computed overlap populations, shows good correlation. Several other points of interest are discussed.
10,417 citations
TL;DR: In this paper, a method of "natural population analysis" was developed to calculate atomic charges and orbital populations of molecular wave functions in general atomic orbital basis sets, which seems to exhibit improved numerical stability and to better describe the electron distribution in compounds of high ionic character.
Abstract: A method of ‘‘natural population analysis’’ has been developed to calculate atomic charges and orbital populations of molecular wave functions in general atomic orbital basis sets. The natural analysis is an alternative to conventional Mulliken population analysis, and seems to exhibit improved numerical stability and to better describe the electron distribution in compounds of high ionic character, such as those containing metal atoms. We calculated ab initio SCF‐MO wave functions for compounds of type CH3X and LiX (X=F, OH, NH2, CH3, BH2, BeH, Li, H) in a variety of basis sets to illustrate the generality of the method, and to compare the natural populations with results of Mulliken analysis, density integration, and empirical measures of ionic character. Natural populations are found to give a satisfactory description of these molecules, providing a unified treatment of covalent and extreme ionic limits at modest computational cost.
9,269 citations
6,478 citations
TL;DR: In this paper, an ab initio method for calculating the electronic structure, electronic transport, and forces acting on the atoms, for atomic scale systems connected to semi-infinite electrodes and with an applied voltage bias.
Abstract: We describe an ab initio method for calculating the electronic structure, electronic transport, and forces acting on the atoms, for atomic scale systems connected to semi-infinite electrodes and with an applied voltage bias. Our method is based on the density-functional theory (DFT) as implemented in the well tested SIESTA approach (which uses nonlocal norm-conserving pseudopotentials to describe the effect of the core electrons, and linear combination of finite-range numerical atomic orbitals to describe the valence states). We fully deal with the atomistic structure of the whole system, treating both the contact and the electrodes on the same footing. The effect of the finite bias (including self-consistency and the solution of the electrostatic problem) is taken into account using nonequilibrium Green's functions. We relate the nonequilibrium Green's function expressions to the more transparent scheme involving the scattering states. As an illustration, the method is applied to three systems where we are able to compare our results to earlier ab initio DFT calculations or experiments, and we point out differences between this method and existing schemes. The systems considered are: (i) single atom carbon wires connected to aluminum electrodes with extended or finite cross section, (ii) single atom gold wires, and finally (iii) large carbon nanotube systems with point defects.
5,634 citations
TL;DR: In this article, the conditions necessary in metals for the presence or absence of localized moments on solute ions containing inner shell electrons are analyzed, and a self-consistent Hartree-Fock treatment is applied to show that there is a sharp transition between the magnetic state and the nonmagnetic state, depending on the density of states of free electrons, the $s\ensuremath{-}d$ admixture matrix elements, and the Coulomb correlation integral in the $d$ shell.
Abstract: The conditions necessary in metals for the presence or absence of localized moments on solute ions containing inner shell electrons are analyzed. A self-consistent Hartree-Fock treatment shows that there is a sharp transition between the magnetic state and the nonmagnetic state, depending on the density of states of free electrons, the $s\ensuremath{-}d$ admixture matrix elements, and the Coulomb correlation integral in the $d$ shell; that in the magnetic state the $d$ polarization can be reduced rather severely to nonintegral values, without appreciable free electron polarization because of a compensation effect; and that in the nonmagnetic state the virtual localized $d$ level tends to lie near the Fermi surface. It is emphasized that the condition for the magnetic state depends on the Coulomb (i.e., exchange self-energy) integral, and that the usual type of exchange alone is not large enough in $d$-shell ions to allow magnetic moments to be present. We show that the susceptibility and specific heat due to the inner shell electrons show strongly contrasting behavior even in the nonmagnetic state. A calculation including degenerate $d$ orbitals and $d\ensuremath{-}d$ exchange shows that the orbital angular momentum can be quenched, even when localized spin moments exist, and even on an isolated magnetic atom, by kinetic energy effects.
5,621 citations
Related Topics (5)
Performance Metrics
| Year | Papers |
|---|---|
| 2026 | 3 |
| 2025 | 190 |
| 2024 | 301 |
| 2023 | 724 |
| 2022 | 1,409 |
| 2021 | 311 |