“Slater determinant”的意思、由来-开放百科全书

In quantum mechanics, a Slater determinant is an expression that describes the wave function of a multi-fermionic system that satisfies anti-symmetry requirements, and consequently the Pauli principle, by changing sign upon exchange of two electrons (or other fermions).^[1] Only a small subset of all possible fermionic wave functions can be written as a single Slater determinant, but those form an important and useful subset because of their simplicity.

The Slater determinant arises from the consideration of a wave function for a collection of electrons, each with a wave function known as the spin-orbital,

, where

denotes the position and spin of a single electron. A Slater determinant containing two electrons with the same spin orbital would correspond to a wave function which is zero everywhere.

The Slater determinant is named for John C. Slater, who introduced the determinant in 1929 as a means of ensuring the antisymmetry of a wave function,^[2] although the wave function in the determinant form first appeared independently in Heisenberg's ^[3] and Dirac's ^[4] papers three years earlier.

Definition

Two-particle case

The simplest way to approximate the wave function of a many-particle system is to take the product of properly chosen orthogonal wave functions of the individual particles. For the two-particle case with coordinates

and

, we have

This expression is used in the Hartree method as an ansatz for the many-particle wave function and is known as a Hartree product. However, it is not satisfactory for fermions because the wave function above is not antisymmetric under exchange of any two of the fermions, as it must be according to the Pauli exclusion principle. An antisymmetric wave function can be mathematically described as follows:

This does not hold for the Hartree product, which therefore does not satisfy the Pauli principle. This problem can be overcome by taking a linear combination of both Hartree products

where the coefficient is the normalization factor. This wave function is now antisymmetric and no longer distinguishes between fermions, that is: one cannot indicate an ordinal number to a specific particle and the indices given are interchangeable. Moreover, it also goes to zero if any two spin orbitals of two fermions are the same. This is equivalent to satisfying the Pauli exclusion principle.

Multi-particle case

The expression can be generalised to any number of fermions by writing it as a determinant. For an N-electron system, the Slater determinant is defined as ^[1]

where in the final expression, a compact notation is introduced: the normalization constant and labels for the fermion coordinates are understood – only the wavefunctions are exhibited. The linear combination of Hartree products for the two-particle case can clearly be seen as identical with the Slater determinant for N = 2. It can be seen that the use of Slater determinants ensures an antisymmetrized function at the outset; other functions are automatically rejected. In the same way, the use of Slater determinants ensures conformity to the Pauli principle. Indeed, the Slater determinant vanishes if the set {χ_i } is linearly dependent. In particular, this is the case when two (or more) spin orbitals are the same. In chemistry one expresses this fact by stating that no two electrons with the same spin can occupy the same spatial orbital. In general the Slater determinant is evaluated by the Laplace expansion. Mathematically, a Slater determinant is an antisymmetric tensor, also known as a wedge product.

As an approximation

Most fermionic wavefunctions cannot be represented as a Slater determinant. The best Slater approximation to a given fermionic wave function can be defined to be the one that maximizes the overlap between the Slater determinant and the target wave function.^[5] The maximal overlap is a geometric measure of entanglement between the fermions.

A single Slater determinant is used as an approximation to the electronic wavefunction in Hartree–Fock theory. In more accurate theories (such as configuration interaction and MCSCF), a linear combination of Slater determinants is needed.

Discussion

The word "detor" was proposed by S. F. Boys to refer to a Slater determinant of orthonormal orbitals,^[6] but this term is rarely used.

Unlike fermions that are subject to the Pauli exclusion principle, two or more bosons can occupy the same single-particle quantum state. Wavefunctions describing systems of identical bosons are symmetric under the exchange of particles and can be expanded in terms of permanents.

See also

References

1. ^¹Molecular Quantum Mechanics Parts I and II: An Introduction to QUANTUM CHEMISTRY (Volume 1), P.W. Atkins, Oxford University Press, 1977, {{ISBN|0-19-855129-0}}
2. ^{{cite journal| last1=Slater| first1=J.| last2=Verma| first2=HC| title=The Theory of Complex Spectra| journal=Physical Review| volume=34| issue=2| pages=1293–1322| year=1929| pmid=9939750| doi=10.1103/PhysRev.34.1293|bibcode = 1929PhRv...34.1293S }}
3. ^{{cite journal |last1 = Heisenberg | first1 = W. | title = Mehrkörperproblem und Resonanz in der Quantenmechanik | journal = Zeitschrift für Physik | year = 1926 | volume = 38 | pages = 411–426| doi= 10.1007/BF01397160|bibcode = 1926ZPhy...38..411H }}
4. ^{{cite journal |last1 = Dirac | first1 = P. A. M. | title = On the Theory of Quantum Mechanics | journal = Proceedings of the Royal Society A | year = 1926 | volume = 112 | pages = 661–677| doi= 10.1098/rspa.1926.0133 |bibcode = 1926RSPSA.112..661D }}
5. ^{{ cite journal|doi=10.1103/PhysRevA.89.012504 | title=Optimal multiconfiguration approximation of an N-fermion wave function |first1=J M |last1=Zhang | first2 = Marcus | last2 = Kollar |page=012504 | volume=89 |year=2014 |journal= Physical Review A |arxiv = 1309.1848 |bibcode = 2014PhRvA..89a2504Z }}
6. ^{{ cite journal| title=Electronic wave functions I. A general method of calculation for the stationary states of any molecular system|author-link=S. Francis Boys|first=S. F. |last=Boys|page=542| volume=A200 |year=1950|journal= Proceedings of the Royal Society}}