Same-spin electron correlation

A paradigmatic application has been reported for ethane [16]. It shows that the Fermi contact contributions to experimental nuclear spin-spin coupling constant are easy to explain in terms of current densities (7.25), which transport spin polarization along the coupling pathway, and associated plots of property density, Eq. (7.57). Same-spin electron correlation, the only kind of correlation recovered by the Hartree Fock wavefunction considered in Ref. [16], determines the alignment of the nuclear dipoles at its ends, as shown in the current-density maps reported for ethane. Fig. 7.44. 

When Hartree-Fock theory fulfills the requirement that 4 be invarient with respect to the exchange of any two electrons by antisymmetrizing the wavefunction, it automatically includes the major correlation effects arising from pairs of electrons with the same spin. This correlation is termed exchange correlation. The motion of electrons of opposite spin remains uncorrelated under Hartree-Fock theory, however. 

The electron density distribution is determined by the electrostatic attraction between the nuclei and the electrons, the electrostatic repulsion between the electrons, the Fermi correlation between same spin electrons (due to the operation of the Pauli principle), and the Coulombic correlation (due to electrostatic repulsion). 

Functionals. The difference between the Fock operator, in wave function based calculations and the analogous operator in DFT calculations is that the Coulomb and exchange operators in T are replaced in DFT by a functional of the electron density. In principle, this functional should provide an exact formula for computing the Coulombic interactions between an electron in a KS orbital and all the other electrons in a molecule. To be exact, this functional must include corrections to the Coulombic repulsion energy, computed directly from the electron density, for exchange between electrons of the same spin and correlation between electrons of opposite spin. 

Now, P ri, V2) = 0. No two electrons with the same spin can be at the same place. This is called the Fermi hole. Thus, same-spin electrons are correlated in Hartree Pock, different-spin electrons are not. Sometimes, it is said that HF methods take into account the so-called spin correlation. 

In a study in 1982, Luken and Culberson analyzed the change of the Fermi hole shape with respect to the position of reference electron to gain information about the spatial localizatirai of electrons [36], The Fermi hole density is derived from the same-spin pair density and describes the probability density to find an electron at given position, when another same-spin electron is localized at the reference position with all the other electros located somewhere in the space. Like in Sect. 2.2, it shows how the electronic motion of electrons creating a same-spin pair is correlated. For a closed-shell Hartree-Fock wave function, the so-called Fermi hole mobility function F(r) ... 

It was claimed that this formulation follows Silvi s approach of spin-pair composition (cf. Sect. 2.10). Indeed, the Laplacian terms are connected with the number of (correlated) same-spin electron pairs in small arbitrary chosen region. However, the... 

Considering instead of ELI-q, the correlated spin-pair composition reveals that for this descriptor the extent of opposite-spin correlation is of minor importance. The spin-pair composition can be seen, similarly to ELI-q, as being based on the q-restricted space partitioning. However, the ratio between the opposite-spin and same-spin electron pairs behaves like the independent opposite-spin pairs would be taken into account (which in this view would in certain sense he proportional to the values of ELI-D see below). 

The ELI variant (ELI-D) based on the correlation between same-spin electrons (described by the Fermi hole) is a robust bonding descriptor directly connected with the Pauli principle. Thus, it can be used already at the independent particle level of theory. ELl-D displays high values in spatial regions that can be connected with the conception of atomic shells, lone pairs, and bonds. In analogy to... 

As a final note, be aware that Hartree-Fock calculations performed with small basis sets are many times more prone to finding unstable SCF solutions than are larger calculations. Sometimes this is a result of spin contamination in other cases, the neglect of electron correlation is at the root. The same molecular system may or may not lead to an instability when it is modeled with a larger basis set or a more accurate method such as Density Functional Theory. Nevertheless, wavefunctions should still be checked for stability with the SCF=Stable option. ... 

Naively it may be expected that the correlation between pairs of electrons belonging to the same spatial MO would be the major part of the electron correlation. However, as the size of the molecule increases, the number of electron pairs belonging to different spatial MOs grows faster than those belonging to the same MO. Consider for example the valence orbitals for CH4. There are four intraorbital electron pairs of opposite spin, but there are 12 interorbital pairs of opposite spin, and 12 interorbital pairs of the same spin. A typical value for the intraorbital pair correlation of a single bond is 20kcal/ mol, while that of an interorbital pair (where the two MO are spatially close, as in CH4) is 1 kcal/mol. The interpair correlation is therefore often comparable to the intrapair contribution. 

Since the coiTelation between opposite spins has both intra- and inter-orbital contributions, it will be larger than the correlation between electrons having the same spin. The Pauli principle (or equivalently the antisymmetry of the wave function) has the consequence that there is no intraorbital conelation from electron pairs with the same spin. The opposite spin correlation is sometimes called the Coulomb correlation, while the same spin correlation is called the Fermi correlation, i.e. the Coulomb correlation is the largest contribution. Another way of looking at electron correlation is in terms of the electron density. In the immediate vicinity of an electron, here is a reduced probability of finding another electron. For electrons of opposite spin, this is often referred to as the Coulomb hole, the corresponding phenomenon for electrons of the same spin is the Fermi hole. 

As mentioned in the start of Chapter 4, the correlation between electrons of parallel spin is different from that between electrons of opposite spin. The exchange energy is by definition given as a sum of contributions from the a and /3 spin densities, as exchange energy only involves electrons of the same spin. The kinetic energy, the nuclear-electron attraction and Coulomb terms are trivially separable. 

Brickstock, A., and Pople, J. A., Phil. Mag. 44, 705, The spatial correlation of electrons in atoms and molecules. IV. The correlation of electrons on a spherical surface." Two examples—four electrons of the same spin and eight paired electrons—have been studied to compare the effects of the exclusion principle and the interelectronic repulsion. 

In the HF scheme, the first origin of the correlation between electrons of antiparallel spins comes from the restriction that they are forced to occupy the same orbital (RHF scheme) and thus some of the same location in space. A simple way of taking into account the basic effects of the electronic correlation is to release the constraint of double occupation (UHF scheme = Unrestricted HF) and so use Different Orbitals for Different Spins (DODS scheme which is the European way of calling UHF). In this methodology, electrons with antiparallel spins are not found to doubly occupy the same orbital so that, in principle, they are not forced to coexist in the same spatial region as is the case in usual RHF wave functions. 

This quantity is of great importance, since it actually contains all information about electron correlation, as we will see presently. Like the density, the pair density is also a non-negative quantity. It is symmetric in the coordinates and normalized to the total number of non-distinct pairs, i. e., N(N-l).8 Obviously, if electrons were identical, classical particles that do not interact at all, such as for example billiard balls of one color, the probability of finding one electron at a particular point of coordinate-spin space would be completely independent of the position and spin of the second electron. Since in our model we view electrons as idealized mass points with no volume, this would even include the possibility that both electrons are simultaneously found in the same volume element. In this case the pair density would reduce to a simple product of the individual probabilities, i.e.,... 

This can only be true if p2 (xj, Xj) = 0. In other words, this result tells us that the probability of finding two electrons with the same spin at the same point in space is exactly zero. Hence, electrons of like spin do not move independently from each other. It is important to realize that this kind of correlation is in no way connected to the charge of the electrons but is a direct consequence of the Pauli principle. It applies equally well to neutral fermions and - also this is very important to keep in mind - does not hold if the two electrons have different spin. This effect is known as exchange or Fermi correlation. As we will show below, this kind of correlation is included in the Hartree-Fock approach due to the antisymmetry of a Slater determinant and therefore has nothing to do with the correlation energy E discussed in the previous chapter. 

Since two electrons of the same spin have a zero probability of occupying the same position in space simultaneously, and since t / is continuous, there is only a small probability of finding two electrons of the same spin close to each other in space, and an increasing probability of finding them an increasingly far apart. In other words the Pauli principle requires electrons with the same spin to keep apart. So the motions of two electrons of the same spin are not independent, but rather are correlated, a phenomenon known as Fermi correlation. Fermi correlation is not to be confused with the Coulombic correlation sometimes referred to without its qualifier simply as correlation . Coulombic correlation results from the Coulombic repulsion between any two electrons, regardless of spin, with the consequent loss of independence of their motion. The Fermi correlation is in most cases much more important than the Coulomb correlation in determining the electron density. 

Equation 4.49 defines the exchange or Fermi hole. It is as if an electron of a given spin digs a hole around itself in space in order to exclude another electron of the same spin from coming near it (Pauli exclusion principle). The integrated hole charge is unity, i.e., there is exactly one electron inside the hole. Likewise, the correlation energy functional can be defined as... 

Hence, the probability of finding one electron with spin a around r and another with spin j3 around r2 is just the product of the probabilities of finding one particle in the given positions. The probabilities are independent, which means that the behavior of electrons is not correlated. However, for the case of two electrons with the same spin ... 

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