Slater determinant

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In quantum mechanics, a Slater determinant is an expression that describes the wave function of a multi-fermionic system. It satisfies anti-symmetry requirements, and consequently the Pauli principle, by changing sign upon exchange of two electrons (or other fermions). 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 ${\displaystyle \chi (\mathbf {x} )}$, where ${\displaystyle \mathbf {x} }$ 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 that 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 many-electron wave function, although the wave function in the determinant form first appeared independently in Heisenberg's and Dirac's articles 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 ${\displaystyle \mathbf {x} _{1}}$ and ${\displaystyle \mathbf {x} _{2}}$, we have

${\displaystyle \Psi (\mathbf {x} _{1},\mathbf {x} _{2})=\chi _{1}(\mathbf {x} _{1})\chi _{2}(\mathbf {x} _{2}).}$

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:

${\displaystyle \Psi (\mathbf {x} _{1},\mathbf {x} _{2})=-\Psi (\mathbf {x} _{2},\mathbf {x} _{1}).}$

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:

${\displaystyle {\begin{aligned}\Psi (\mathbf {x} _{1},\mathbf {x} _{2})&={\frac {1}{\sqrt {2}}}\{\chi _{1}(\mathbf {x} _{1})\chi _{2}(\mathbf {x} _{2})-\chi _{1}(\mathbf {x} _{2})\chi _{2}(\mathbf {x} _{1})\}\\&={\frac {1}{\sqrt {2}}}{\begin{vmatrix}\chi _{1}(\mathbf {x} _{1})&\chi _{2}(\mathbf {x} _{1})\\\chi _{1}(\mathbf {x} _{2})&\chi _{2}(\mathbf {x} _{2})\end{vmatrix}},\end{aligned}}}$

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

${\displaystyle {\begin{aligned}\Psi (\mathbf {x} _{1},\mathbf {x} _{2},\ldots ,\mathbf {x} _{N})&={\frac {1}{\sqrt {N!}}}{\begin{vmatrix}\chi _{1}(\mathbf {x} _{1})&\chi _{2}(\mathbf {x} _{1})&\cdots &\chi _{N}(\mathbf {x} _{1})\\\chi _{1}(\mathbf {x} _{2})&\chi _{2}(\mathbf {x} _{2})&\cdots &\chi _{N}(\mathbf {x} _{2})\\\vdots &\vdots &\ddots &\vdots \\\chi _{1}(\mathbf {x} _{N})&\chi _{2}(\mathbf {x} _{N})&\cdots &\chi _{N}(\mathbf {x} _{N})\end{vmatrix}}\\&\equiv |\chi _{1},\chi _{2},\cdots ,\chi _{N}\rangle \\&\equiv |1,2,\dots ,N\rangle ,\end{aligned}}}$

where the last two expressions use a shorthand for Slater determinants: The normalization constant is implied by noting the number N, and only the one-particle wavefunctions (first shorthand) or the indices for the fermion coordinates (second shorthand) are written down. All skipped labels are implied to behave in ascending sequence. The linear combination of Hartree products for the two-particle case is identical with the Slater determinant for N = 2. The use of Slater determinants ensures an antisymmetrized function at the outset. In the same way, the use of Slater determinants ensures conformity to the Pauli principle. Indeed, the Slater determinant vanishes if the set ${\displaystyle \{\chi _{i}\}}$ 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.

Example: Matrix elements in a many electron problem

Many properties of the Slater determinant come to life with an example in a non-relativistic many electron problem.

• The one particle terms of the Hamiltonian will contribute in the same manner as for the simple Hartree product, namely the energy is summed and the states are independent
• The multi-particle terms of the Hamiltonian, i.e. the exchange terms, will introduce a lowering of the energy of the eigenstates

Starting from an Hamiltonian:

$${\displaystyle {\hat {H}}_{\text{tot}}=\sum _{i}{\frac {\mathbf {p} _{i}^{2}}{2m}}+\sum _{I}{\frac {\mathbf {P} _{I}^{2}}{2M_{I}}}+\sum _{i}V_{\text{nucl}}(\mathbf {r_{i}} )+{\frac {1}{2}}\sum _{i\neq j}{\frac {e^{2}}{|\mathbf {r} _{i}-\mathbf {r} _{j}|}}+{\frac {1}{2}}\sum _{I\neq J}{\frac {Z_{I}Z_{J}e^{2}}{|\mathbf {R} _{I}-\mathbf {R} _{J}|}}}$$

where ${\displaystyle \mathbf {r} _{i}}$ are the electrons and ${\displaystyle \mathbf {R} _{I}}$are the nuclei and

${\displaystyle V_{\text{nucl}}(\mathbf {r} )=-\sum _{I}{\frac {Z_{I}e^{2}}{|\mathbf {r} -\mathbf {R} _{I}|}}}$

For simplicity we freeze the nuclei at equilibrium in one position and we remain with a simplified Hamiltonian

${\displaystyle {\hat {H}}_{e}=\sum _{i}^{N}{\hat {h}}(\mathbf {r} _{i})+{\frac {1}{2}}\sum _{i\neq j}^{N}{\frac {e^{2}}{r_{ij}}}}$

where

${\displaystyle {\hat {h}}(\mathbf {r} )={\frac {{\hat {\mathbf {p} }}^{2}}{2m}}+V_{\text{nucl}}(\mathbf {r} )}$

and where we will distinguish in the Hamiltonian between the first set of terms as ${\displaystyle {\hat {G}}_{1}}$ (the "1" particle terms) and the last term ${\displaystyle {\hat {G}}_{2}}$ which is the "2" particle term or exchange term

${\displaystyle {\hat {G}}_{1}=\sum _{i}^{N}{\hat {h}}(\mathbf {r} _{i})}$

${\displaystyle {\hat {G}}_{2}={\frac {1}{2}}\sum _{i\neq j}^{N}{\frac {e^{2}}{r_{ij}}}}$

The two parts will behave differently when they have to interact with a Slater determinant wave function. We start to compute the expectation values

${\displaystyle \langle \Psi _{0}|G_{1}|\Psi _{0}\rangle ={\frac {1}{N!}}\langle \det\{\psi _{1}...\psi _{N}\}|G_{1}|\det\{\psi _{1}...\psi _{N}\}\rangle }$

In the above expression, we can just select the identical permutation in the determinant in the left part, since all the other N! − 1 permutations would give the same result as the selected one. We can thus cancel N! at the denominator

${\displaystyle \langle \Psi _{0}|G_{1}|\Psi _{0}\rangle =\langle \psi _{1}...\psi _{N}|G_{1}|\det\{\psi _{1}...\psi _{N}\}\rangle }$

Because of the orthonormality of spin-orbitals it is also evident that only the identical permutation survives in the determinant on the right part of the above matrix element

${\displaystyle \langle \Psi _{0}|G_{1}|\Psi _{0}\rangle =\langle \psi _{1}...\psi _{N}|G_{1}|\psi _{1}...\psi _{N}\rangle }$

This result shows that the anti-symmetrization of the product does not have any effect for the one particle terms and it behaves as it would do in the case of the simple Hartree product.

And finally we remain with the trace over the one particle Hamiltonians

${\displaystyle \langle \Psi _{0}|G_{1}|\Psi _{0}\rangle =\sum _{i}\langle \psi _{i}|h|\psi _{i}\rangle }$

Which tells us that to the extent of the one particle terms the wave functions of the electrons are independent of each other and the energy is given by the sum of energies of the single particles.

For the exchange part instead

${\displaystyle \langle \Psi _{0}|G_{2}|\Psi _{0}\rangle ={\frac {1}{N!}}\langle \det\{\psi _{1}...\psi _{N}\}|G_{2}|\det\{\psi _{1}...\psi _{N}\}\rangle =\langle \psi _{1}...\psi _{N}|G_{2}|\det\{\psi _{1}...\psi _{N}\}\rangle }$

If we see the action of one exchange term it will select only the exchanged wavefunctions

${\displaystyle \langle \psi _{1}(r_{1},\sigma _{1})...\psi _{N}(r_{N},\sigma _{N})|{\frac {e^{2}}{r_{12}}}|\mathrm {det} \{\psi _{1}(r_{1},\sigma _{1})...\psi _{N}(r_{N},\sigma _{N})\}\rangle =\langle \psi _{1}\psi _{2}|{\frac {e^{2}}{r_{12}}}|\psi _{1}\psi _{2}\rangle -\langle \psi _{1}\psi _{2}|{\frac {e^{2}}{r_{12}}}|\psi _{2}\psi _{1}\rangle }$

And finally

$${\displaystyle \langle \Psi _{0}|G_{2}|\Psi _{0}\rangle ={\frac {1}{2}}\sum _{ij}\left[\langle \psi _{i}\psi _{j}|{\frac {e^{2}}{r_{ij}}}|\psi _{i}\psi _{j}\rangle -\langle \psi _{i}\psi _{j}|{\frac {e^{2}}{r_{ij}}}|\psi _{j}\psi _{i}\rangle \right]}$$

which instead is a mixing term, the first contribution is called "coulomb" term and the second is the "exchange" term which can be written using ${\textstyle \sum _{ij}}$ or ${\textstyle \sum _{i\neq j}}$, since the Coulomb and exchange contributions exactly cancel each other for ${\displaystyle i=j}$.

It is important to notice explicitly that the electron-electron repulsive energy ${\displaystyle \langle \Psi _{0}|G_{2}|\Psi _{0}\rangle }$ on the antisymmetrized product of spin-orbitals is always lower than the electron-electron repulsive energy on the simple Hartree product of the same spin-orbitals. The difference is just represented by the second term in the right-hand side without the self-interaction terms ${\displaystyle i=j}$. Since exchange bielectronic integrals are positive quantities, different from zero only for spin-orbitals with parallel spins, we link the decrease in energy with the physical fact that electrons with parallel spin are kept apart in real space in Slater determinant states.

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. 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, 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.

Mechanics

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Mechanics (from Ancient Greek: μηχανική, mēkhanikḗ, lit. "of machines") is the area of mathematics and physics concerned with the relationships between force, matter, and motion among physical objects. Forces applied to objects result in displacements, or changes of an object's position relative to its environment.

Theoretical expositions of this branch of physics has its origins in Ancient Greece, for instance, in the writings of Aristotle and Archimedes (see History of classical mechanics and Timeline of classical mechanics). During the early modern period, scientists such as Galileo, Kepler, Huygens, and Newton laid the foundation for what is now known as classical mechanics.

As a branch of classical physics, mechanics deals with bodies that are either at rest or are moving with velocities significantly less than the speed of light. It can also be defined as the physical science that deals with the motion of and forces on bodies not in the quantum realm.

History

Main articles: History of classical mechanics and History of quantum mechanics

Antiquity

Main article: Aristotelian mechanics

The ancient Greek philosophers were among the first to propose that abstract principles govern nature. The main theory of mechanics in antiquity was Aristotelian mechanics, though an alternative theory is exposed in the pseudo-Aristotelian Mechanical Problems, often attributed to one of his successors.

There is another tradition that goes back to the ancient Greeks where mathematics is used more extensively to analyze bodies statically or dynamically, an approach that may have been stimulated by prior work of the Pythagorean Archytas. Examples of this tradition include pseudo-Euclid (On the Balance), Archimedes (On the Equilibrium of Planes, On Floating Bodies), Hero (Mechanica), and Pappus (Collection, Book VIII).

Medieval age

Main article: Theory of impetus

 

Arabic machine in a manuscript of unknown date.

In the Middle Ages, Aristotle's theories were criticized and modified by a number of figures, beginning with John Philoponus in the 6th century. A central problem was that of projectile motion, which was discussed by Hipparchus and Philoponus.

Persian Islamic polymath Ibn Sīnā published his theory of motion in The Book of Healing (1020). He said that an impetus is imparted to a projectile by the thrower, and viewed it as persistent, requiring external forces such as air resistance to dissipate it. Ibn Sina made distinction between 'force' and 'inclination' (called "mayl"), and argued that an object gained mayl when the object is in opposition to its natural motion. So he concluded that continuation of motion is attributed to the inclination that is transferred to the object, and that object will be in motion until the mayl is spent. He also claimed that a projectile in a vacuum would not stop unless it is acted upon, consistent with Newton's first law of motion.

On the question of a body subject to a constant (uniform) force, the 12th-century Jewish-Arab scholar Hibat Allah Abu'l-Barakat al-Baghdaadi (born Nathanel, Iraqi, of Baghdad) stated that constant force imparts constant acceleration. According to Shlomo Pines, al-Baghdaadi's theory of motion was "the oldest negation of Aristotle's fundamental dynamic law [namely, that a constant force produces a uniform motion], [and is thus an] anticipation in a vague fashion of the fundamental law of classical mechanics [namely, that a force applied continuously produces acceleration]."

Influenced by earlier writers such as Ibn Sina and al-Baghdaadi, the 14th-century French priest Jean Buridan developed the theory of impetus, which later developed into the modern theories of inertia, velocity, acceleration and momentum. This work and others was developed in 14th-century England by the Oxford Calculators such as Thomas Bradwardine, who studied and formulated various laws regarding falling bodies. The concept that the main properties of a body are uniformly accelerated motion (as of falling bodies) was worked out by the 14th-century Oxford Calculators.

Early modern age

First European depiction of a piston pump, by Taccola, c. 1450.

Two central figures in the early modern age are Galileo Galilei and Isaac Newton. Galileo's final statement of his mechanics, particularly of falling bodies, is his Two New Sciences (1638). Newton's 1687 Philosophiæ Naturalis Principia Mathematica provided a detailed mathematical account of mechanics, using the newly developed mathematics of calculus and providing the basis of Newtonian mechanics.

There is some dispute over priority of various ideas: Newton's Principia is certainly the seminal work and has been tremendously influential, and many of the mathematics results therein could not have been stated earlier without the development of the calculus. However, many of the ideas, particularly as pertain to inertia and falling bodies, had been developed by prior scholars such as Christiaan Huygens and the less-known medieval predecessors. Precise credit is at times difficult or contentious because scientific language and standards of proof changed, so whether medieval statements are equivalent to modern statements or sufficient proof, or instead similar to modern statements and hypotheses is often debatable.

Modern age

Two main modern developments in mechanics are general relativity of Einstein, and quantum mechanics, both developed in the 20th century based in part on earlier 19th-century ideas. The development in the modern continuum mechanics, particularly in the areas of elasticity, plasticity, fluid dynamics, electrodynamics and thermodynamics of deformable media, started in the second half of the 20th century.

Types of mechanical bodies

The often-used term body needs to stand for a wide assortment of objects, including particles, projectiles, spacecraft, stars, parts of machinery, parts of solids, parts of fluids (gases and liquids), etc.

Other distinctions between the various sub-disciplines of mechanics, concern the nature of the bodies being described. Particles are bodies with little (known) internal structure, treated as mathematical points in classical mechanics. Rigid bodies have size and shape, but retain a simplicity close to that of the particle, adding just a few so-called degrees of freedom, such as orientation in space.

Otherwise, bodies may be semi-rigid, i.e. elastic, or non-rigid, i.e. fluid. These subjects have both classical and quantum divisions of study.

For instance, the motion of a spacecraft, regarding its orbit and attitude (rotation), is described by the relativistic theory of classical mechanics, while the analogous movements of an atomic nucleus are described by quantum mechanics.

Sub-disciplines

The following are two lists of various subjects that are studied in mechanics.

Note that there is also the "theory of fields" which constitutes a separate discipline in physics, formally treated as distinct from mechanics, whether classical fields or quantum fields. But in actual practice, subjects belonging to mechanics and fields are closely interwoven. Thus, for instance, forces that act on particles are frequently derived from fields (electromagnetic or gravitational), and particles generate fields by acting as sources. In fact, in quantum mechanics, particles themselves are fields, as described theoretically by the wave function.

Classical

The following are described as forming classical mechanics:

• Newtonian mechanics, the original theory of motion (kinematics) and forces (dynamics).
• Analytical mechanics is a reformulation of Newtonian mechanics with an emphasis on system energy, rather than on forces. There are two main branches of analytical mechanics:
  • Hamiltonian mechanics, a theoretical formalism, based on the principle of conservation of energy.
  • Lagrangian mechanics, another theoretical formalism, based on the principle of the least action.
• Classical statistical mechanics generalizes ordinary classical mechanics to consider systems in an unknown state; often used to derive thermodynamic properties.
• Celestial mechanics, the motion of bodies in space: planets, comets, stars, galaxies, etc.
• Astrodynamics, spacecraft navigation, etc.
• Solid mechanics, elasticity, plasticity, viscoelasticity exhibited by deformable solids.
• Fracture mechanics
• Acoustics, sound ( = density variation propagation) in solids, fluids and gases.
• Statics, semi-rigid bodies in mechanical equilibrium
• Fluid mechanics, the motion of fluids
• Soil mechanics, mechanical behavior of soils
• Continuum mechanics, mechanics of continua (both solid and fluid)
• Hydraulics, mechanical properties of liquids
• Fluid statics, liquids in equilibrium
• Applied mechanics, or Engineering mechanics
• Biomechanics, solids, fluids, etc. in biology
• Biophysics, physical processes in living organisms
• Relativistic or Einsteinian mechanics, universal gravitation.

Quantum

The following are categorized as being part of quantum mechanics:

• Schrödinger wave mechanics, used to describe the movements of the wavefunction of a single particle.
• Matrix mechanics is an alternative formulation that allows considering systems with a finite-dimensional state space.
• Quantum statistical mechanics generalizes ordinary quantum mechanics to consider systems in an unknown state; often used to derive thermodynamic properties.
• Particle physics, the motion, structure, and reactions of particles
• Nuclear physics, the motion, structure, and reactions of nuclei
• Condensed matter physics, quantum gases, solids, liquids, etc.

Historically, classical mechanics had been around for nearly a quarter millennium before quantum mechanics developed. Classical mechanics originated with Isaac Newton's laws of motion in Philosophiæ Naturalis Principia Mathematica, developed over the seventeenth century. Quantum mechanics developed later, over the nineteenth century, precipitated by Planck's postulate and Albert Einstein's explanation of the photoelectric effect. Both fields are commonly held to constitute the most certain knowledge that exists about physical nature.

Classical mechanics has especially often been viewed as a model for other so-called exact sciences. Essential in this respect is the extensive use of mathematics in theories, as well as the decisive role played by experiment in generating and testing them.

Quantum mechanics is of a bigger scope, as it encompasses classical mechanics as a sub-discipline which applies under certain restricted circumstances. According to the correspondence principle, there is no contradiction or conflict between the two subjects, each simply pertains to specific situations. The correspondence principle states that the behavior of systems described by quantum theories reproduces classical physics in the limit of large quantum numbers, i.e. if quantum mechanics is applied to large systems (for e.g. a baseball), the result would almost be the same if classical mechanics had been applied. Quantum mechanics has superseded classical mechanics at the foundation level and is indispensable for the explanation and prediction of processes at the molecular, atomic, and sub-atomic level. However, for macroscopic processes classical mechanics is able to solve problems which are unmanageably difficult (mainly due to computational limits) in quantum mechanics and hence remains useful and well used. Modern descriptions of such behavior begin with a careful definition of such quantities as displacement (distance moved), time, velocity, acceleration, mass, and force. Until about 400 years ago, however, motion was explained from a very different point of view. For example, following the ideas of Greek philosopher and scientist Aristotle, scientists reasoned that a cannonball falls down because its natural position is in the Earth; the sun, the moon, and the stars travel in circles around the earth because it is the nature of heavenly objects to travel in perfect circles.

Often cited as father to modern science, Galileo brought together the ideas of other great thinkers of his time and began to calculate motion in terms of distance travelled from some starting position and the time that it took. He showed that the speed of falling objects increases steadily during the time of their fall. This acceleration is the same for heavy objects as for light ones, provided air friction (air resistance) is discounted. The English mathematician and physicist Isaac Newton improved this analysis by defining force and mass and relating these to acceleration. For objects traveling at speeds close to the speed of light, Newton's laws were superseded by Albert Einstein's theory of relativity. [A sentence illustrating the computational complication of Einstein's theory of relativity.] For atomic and subatomic particles, Newton's laws were superseded by quantum theory. For everyday phenomena, however, Newton's three laws of motion remain the cornerstone of dynamics, which is the study of what causes motion.

Relativistic

In analogy to the distinction between quantum and classical mechanics, Albert Einstein's general and special theories of relativity have expanded the scope of Newton and Galileo's formulation of mechanics. The differences between relativistic and Newtonian mechanics become significant and even dominant as the velocity of a body approaches the speed of light. For instance, in Newtonian mechanics, the kinetic energy of a free particle is E=1/2mv², whereas in relativistic mechanics, it is E = (γ-1)mc² (where γ is the Lorentz factor; this formula reduces to the Newtonian expression in the low energy limit).

For high-energy processes, quantum mechanics must be adjusted to account for special relativity; this has led to the development of quantum field theory.

Professional organizations

• Applied Mechanics Division, American Society of Mechanical Engineers
• Fluid Dynamics Division, American Physical Society
• Society for Experimental Mechanics
• Institution of Mechanical Engineers is the United Kingdom's qualifying body for mechanical engineers and has been the home of Mechanical Engineers for over 150 years.
• International Union of Theoretical and Applied Mechanics