Density atomic orbital

The calculation proceeds as illustrated in Table 2.2, which shows the variation in the coefficients of the atomic orbitals in the lowest-energy wavefunction and the energy for the first four SCF iterations. The energy is converged to six decimal places after six iterations and the charge density matrix after nine iterations. 

Highest occupied molecular orbital Intermediate neglect of differential overlap Linear combination of atomic orbitals Local density approximation Local spin density functional theory Lowest unoccupied molecular orbital Many-body perturbation theory Modified INDO version 3 Modified neglect of diatomic overlap Molecular orbital Moller-Plesset... 

The origins of the Finnis-Sinclair potential [Finnis and Sinclair 1984] lie in the density of states and the moments theorem. Recall that the density of states D(E) (see Section 3.8.5) describes the distribution of electronic states in the system. D(E) gives the number of states between E and E - - 8E. Such a distribution can be described in terms of its moments. The moments are usually defined relative to the energy of the atomic orbital from which the molecular orbitals are formed. The mth moment, fi", is given by ... 

LCAO (linear combination of atomic orbitals) refers to construction of a wave function from atomic basis functions LDA (local density approximation) approximation used in some of the more approximate DFT methods... 

The neglect of electron-electron interactions in the Extended Hiickel model has several consequences. For example, the atomic orbital binding energies are fixed and do not depend on charge density. With the more accurate NDO semi-empirical treatments, these energies are appropriately sensitive to the surrounding molecular environment. 

The Extended Hiickel method neglects all electron-electron interactions. More accurate calculations are possible with HyperChem by using methods that neglect some, but not all, of the electron-electron interactions. These methods are called Neglect of Differential Overlap or NDO methods. In some parts of the calculation they neglect the effects of any overlap density between atomic orbitals. This reduces the number of electron-electron interaction integrals to calculate, which would otherwise be too time-consuming for all but the smallest molecules. 

The spacial distribution of electron density in an atom is described by means of atomic orbitals Vr(r, 6, (p) such that for a given orbital xp the function xj/ dv gives the probability of finding the electron in an element of volume dv at a point having the polar coordinates r, 6, 0. Each orbital can be expressed as a product of two functions, i e. 0, [Pg.1285]

The usefulness of spin density surfaces can be seen in the following models of methyl radical, CH3, and allyl radical, CH2=CHCH2. In each case, the surface is shaped somewhat like a 2p atomic orbital on carbon. There are some interesting differences between the two radicals, however. While the unpaired electron is confined to the carbon atom in methyl radical, it is delocalized over the two terminal carbons in allyl radical. 

When working with atomic orbitals, it is usual to write the electron density in terms of a certain matrix called (not surprisingly) the electron density matrix. For the simple dihydrogen VB wavefunction, we have... 

Atomic orbital Isa is associated with nucleus Ha and atomic orbital Isb with nucleus Hb. The first term in the electron density (is (r)) /(I -I-S ab) is taken to represent the amount of electron density associated with nucleus Ha- The corresponding term (ls (r)) /(I -I-S ab) represents the electron density associated with nucleus Hb and the remainder 2(lsA(r)lsB(r))/(l -t- AB) is taken to represent the amount shared by the two nuclei. Mulliken s first idea was to integrate these contributions, which gives the values 1/(1 -I-S ab), 1/(1 fi- AB) and (25ab)/(1 + ab). These values are assumed to contain some chemical information. Note that they sum to 2, the number of electrons in H2. 

There is a second point to note in dementi s paper above where he speaks of 3d and 4f functions. These atomic orbitals play no part in the description of atomic electronic ground states for first- and second-row atoms, but on molecule formation the atomic electron density distorts and such polarization functions are needed to accurately describe the distortion. 

Carbon atoms in free space have spherical symmetry, but a carbon atom in a molecule is a quite different entity because its charge density may well distort from spherical symmetry. To take account of the finer points of this distortion, we very often need to include d, f,. .. atomic orbitals in the basis set. Such atomic orbitals are referred to as polarization functions because their inclusion would allow a free atom to take account of the polarization induced by an external electric field or by molecule formation. 1 mentioned polarization functions briefly in Section 9.3.1. 

The concept of natural orbitals may be used for distributing electrons into atomic and molecular orbitals, and thereby for deriving atomic charges and molecular bonds. The idea in the Natural Atomic Orbital (NAO) and Natural Bond Orbital (NBO) analysis developed by F. Weinholt and co-workers " is to use the one-electron density matrix for defining the shape of the atomic orbitals in the molecular environment, and derive molecular bonds from electron density between atoms. 

Here A and B denote atoms in each of the two interacting molecules. The V operator contains all the potential energy operators from both molecules, and the (xa V xb) integral is basically a resonance type integral between two atomic orbitals, one from each molecule. The pa is the electron density on atom A, and the first term in (15.1)... 

But alas most of what has been described so far concerning density theory applies in theory rather than in practice. The fact that the Thomas-Fermi method is capable of yielding a universal solution for all atoms in the periodic table is a potentially attractive feature but is generally not realized in practice. The attempts to implement the ideas originally due to Thomas and Fermi have not quite materialized. This has meant a return to the need to solve a number of equations separately for each individual atom as one does in the Hartree-Fock method and other ab initio methods using atomic orbitals. 

In addition most of the more tractable approaches in density functional theory also involve a return to the use of atomic orbitals in carrying out quantum mechanical calculations since there is no known means of directly obtaining the functional that captures electron density exactly. The work almost invariably falls back on using basis sets of atomic orbitals which means that conceptually we are back to square one and that the promise of density functional methods to work with observable electron density, has not materialized. 

This is why I and some others have been agitating about the recent reports, starting in Nature magazine in September 1999, that atomic orbitals had been directly observed. This is simply impossible unless one is using the word "orbital" rather perversely to mean charge density (Scerri, 2000). 

Figure 2.14. The molecular orbitals of gas phase carbon monoxide, (a) Energy diagram indicating how the molecular orbitals arise from the combination of atomic orbitals of carbon (C) and oxygen (O). Conventional arrows are used to indicate the spin orientations of electrons in the occupied orbitals. Asterisks denote antibonding molecular orbitals, (b) Spatial distributions of key orbitals involved in the chemisorption of carbon monoxide. Barring indicates empty orbitals.5 (c) Electronic configurations of CO and NO in vacuum as compared to the density of states of a Pt(lll) cluster.11 Reprinted from ref. 11 with permission from Elsevier Science.

Tj FIGURE 1.33 The three s-orbitals of 5 lowest energy. The simplest way of drawing an atomic orbital is as a g boundary surface, a surface within which there is a high probability (typically 90%) of finding the electron. We shall use blue to denote s-orbitals, but that color is only an aid to their identification. The shading Jp within the boundary surfaces is an 9 approximate indication of the electron density at each point. 

To improve our model we note that s- and /7-orbitals are waves of electron density centered on the nucleus of an atom. We imagine that the four orbitals interfere with one another and produce new patterns where they intersect, like waves in water. Where the wavefunctions are all positive or all negative, the amplitudes are increased by this interference where the wavefunctions have opposite signs, the overall amplitude is reduced and might even be canceled completely. As a result, the interference between the atomic orbitals results in new patterns. These new patterns are called hybrid orbitals. Each of the four hybrid orbitals, designated bn, is formed from a linear combinations of the four atomic orbitals ... 

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