Boltzmann equation

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Boltzmann_equation 

 

The place of the Boltzmann kinetic equation on the stairs of model reduction from microscopic dynamics to macroscopic continuum dynamics (illustration to the content of the book)

The Boltzmann equation or Boltzmann transport equation (BTE) describes the statistical behaviour of a thermodynamic system not in a state of equilibrium, devised by Ludwig Boltzmann in 1872. The classic example of such a system is a fluid with temperature gradients in space causing heat to flow from hotter regions to colder ones, by the random but biased transport of the particles making up that fluid. In the modern literature the term Boltzmann equation is often used in a more general sense, referring to any kinetic equation that describes the change of a macroscopic quantity in a thermodynamic system, such as energy, charge or particle number.

The equation arises not by analyzing the individual positions and momenta of each particle in the fluid but rather by considering a probability distribution for the position and momentum of a typical particle—that is, the probability that the particle occupies a given very small region of space (mathematically the volume element ${\displaystyle \mathrm {d} ^{3}{\bf {r}}}$) centered at the position ${\displaystyle {\bf {r}}}$, and has momentum nearly equal to a given momentum vector ${\displaystyle {\bf {p}}}$ (thus occupying a very small region of momentum space ${\displaystyle \mathrm {d} ^{3}{\bf {p}}}$), at an instant of time.

The Boltzmann equation can be used to determine how physical quantities change, such as heat energy and momentum, when a fluid is in transport. One may also derive other properties characteristic to fluids such as viscosity, thermal conductivity, and electrical conductivity (by treating the charge carriers in a material as a gas).

The equation is a nonlinear integro-differential equation, and the unknown function in the equation is a probability density function in six-dimensional space of a particle position and momentum. The problem of existence and uniqueness of solutions is still not fully resolved, but some recent results are quite promising.

Overview

The phase space and density function

The set of all possible positions r and momenta p is called the phase space of the system; in other words a set of three coordinates for each position coordinate x, y, z, and three more for each momentum component p_x, p_y, p_z. The entire space is 6-dimensional: a point in this space is (r, p) = (x, y, z, p_x, p_y, p_z), and each coordinate is parameterized by time t. The small volume ("differential volume element") is written

${\displaystyle {\text{d}}^{3}\mathbf {r} \,{\text{d}}^{3}\mathbf {p} ={\text{d}}x\,{\text{d}}y\,{\text{d}}z\,{\text{d}}p_{x}\,{\text{d}}p_{y}\,{\text{d}}p_{z}.}$

Since the probability of N molecules which all have r and p within ${\displaystyle \mathrm {d} ^{3}{\bf {r}}}$ ${\displaystyle \mathrm {d} ^{3}{\bf {p}}}$ is in question, at the heart of the equation is a quantity f which gives this probability per unit phase-space volume, or probability per unit length cubed per unit momentum cubed, at an instant of time t. This is a probability density function: f(r, p, t), defined so that,

${\displaystyle {\text{d}}N=f(\mathbf {r} ,\mathbf {p} ,t)\,{\text{d}}^{3}\mathbf {r} \,{\text{d}}^{3}\mathbf {p} }$

is the number of molecules which all have positions lying within a volume element ${\displaystyle d^{3}{\bf {r}}}$ about r and momenta lying within a momentum space element ${\displaystyle \mathrm {d} ^{3}{\bf {p}}}$ about p, at time t. Integrating over a region of position space and momentum space gives the total number of particles which have positions and momenta in that region:

${\displaystyle {\begin{aligned}N&=\int \limits _{\mathrm {momenta} }{\text{d}}^{3}\mathbf {p} \int \limits _{\mathrm {positions} }{\text{d}}^{3}\mathbf {r} \,f(\mathbf {r} ,\mathbf {p} ,t)\\[5pt]&=\iiint \limits _{\mathrm {momenta} }\quad \iiint \limits _{\mathrm {positions} }f(x,y,z,p_{x},p_{y},p_{z},t)\,{\text{d}}x\,{\text{d}}y\,{\text{d}}z\,{\text{d}}p_{x}\,{\text{d}}p_{y}\,{\text{d}}p_{z}\end{aligned}}}$

which is a 6-fold integral. While f is associated with a number of particles, the phase space is for one-particle (not all of them, which is usually the case with deterministic many-body systems), since only one r and p is in question. It is not part of the analysis to use r₁, p₁ for particle 1, r₂, p₂ for particle 2, etc. up to r_N, p_N for particle N.

It is assumed the particles in the system are identical (so each has an identical mass m). For a mixture of more than one chemical species, one distribution is needed for each, see below.

Principal statement

The general equation can then be written as

${\displaystyle {\frac {df}{dt}}=\left({\frac {\partial f}{\partial t}}\right)_{\text{force}}+\left({\frac {\partial f}{\partial t}}\right)_{\text{diff}}+\left({\frac {\partial f}{\partial t}}\right)_{\text{coll}},}$

where the "force" term corresponds to the forces exerted on the particles by an external influence (not by the particles themselves), the "diff" term represents the diffusion of particles, and "coll" is the collision term – accounting for the forces acting between particles in collisions. Expressions for each term on the right side are provided below.

Note that some authors use the particle velocity v instead of momentum p; they are related in the definition of momentum by p = mv.

The force and diffusion terms

Consider particles described by f, each experiencing an external force F not due to other particles (see the collision term for the latter treatment).

Suppose at time t some number of particles all have position r within element ${\displaystyle d^{3}{\bf {r}}}$ and momentum p within ${\displaystyle d^{3}{\bf {p}}}$. If a force F instantly acts on each particle, then at time t + Δt their position will be r + Δr = r + pΔt/m and momentum p + Δp = p + FΔt. Then, in the absence of collisions, f must satisfy

${\displaystyle f\left(\mathbf {r} +{\frac {\mathbf {p} }{m}}\,\Delta t,\mathbf {p} +\mathbf {F} \,\Delta t,t+\Delta t\right)\,d^{3}\mathbf {r} \,d^{3}\mathbf {p} =f(\mathbf {r} ,\mathbf {p} ,t)\,d^{3}\mathbf {r} \,d^{3}\mathbf {p} }$

Note that we have used the fact that the phase space volume element ${\displaystyle d^{3}{\bf {r}}}$ ${\displaystyle d^{3}{\bf {p}}}$ is constant, which can be shown using Hamilton's equations (see the discussion under Liouville's theorem). However, since collisions do occur, the particle density in the phase-space volume ${\displaystyle d^{3}{\bf {r}}}$ '${\displaystyle d^{3}{\bf {p}}}$ changes, so

${\displaystyle {\begin{aligned}dN_{\mathrm {coll} }&=\left({\frac {\partial f}{\partial t}}\right)_{\mathrm {coll} }\Delta td^{3}\mathbf {r} d^{3}\mathbf {p} \\[5pt]&=f\left(\mathbf {r} +{\frac {\mathbf {p} }{m}}\Delta t,\mathbf {p} +\mathbf {F} \Delta t,t+\Delta t\right)d^{3}\mathbf {r} d^{3}\mathbf {p} -f(\mathbf {r} ,\mathbf {p} ,t)\,d^{3}\mathbf {r} \,d^{3}\mathbf {p} \\[5pt]&=\Delta f\,d^{3}\mathbf {r} \,d^{3}\mathbf {p} \end{aligned}}}$

(1)

where Δf is the total change in f. Dividing (1) by ${\displaystyle d^{3}{\bf {r}}}$ ${\displaystyle d^{3}{\bf {p}}}$ Δt and taking the limits Δt → 0 and Δf → 0, we have

${\displaystyle {\frac {df}{dt}}=\left({\frac {\partial f}{\partial t}}\right)_{\mathrm {coll} }}$

(2)

The total differential of f is:

${\displaystyle {\begin{aligned}df&={\frac {\partial f}{\partial t}}\,dt+\left({\frac {\partial f}{\partial x}}\,dx+{\frac {\partial f}{\partial y}}\,dy+{\frac {\partial f}{\partial z}}\,dz\right)+\left({\frac {\partial f}{\partial p_{x}}}\,dp_{x}+{\frac {\partial f}{\partial p_{y}}}\,dp_{y}+{\frac {\partial f}{\partial p_{z}}}\,dp_{z}\right)\\[5pt]&={\frac {\partial f}{\partial t}}dt+\nabla f\cdot d\mathbf {r} +{\frac {\partial f}{\partial \mathbf {p} }}\cdot d\mathbf {p} \\[5pt]&={\frac {\partial f}{\partial t}}dt+\nabla f\cdot {\frac {\mathbf {p} }{m}}dt+{\frac {\partial f}{\partial \mathbf {p} }}\cdot \mathbf {F} \,dt\end{aligned}}}$

(3)

where ∇ is the gradient operator, · is the dot product,

${\displaystyle {\frac {\partial f}{\partial \mathbf {p} }}=\mathbf {\hat {e}} _{x}{\frac {\partial f}{\partial p_{x}}}+\mathbf {\hat {e}} _{y}{\frac {\partial f}{\partial p_{y}}}+\mathbf {\hat {e}} _{z}{\frac {\partial f}{\partial p_{z}}}=\nabla _{\mathbf {p} }f}$

is a shorthand for the momentum analogue of ∇, and ê_x, ê_y, ê_z are Cartesian unit vectors.

Final statement

Dividing (3) by dt and substituting into (2) gives:

${\displaystyle {\frac {\partial f}{\partial t}}+{\frac {\mathbf {p} }{m}}\cdot \nabla f+\mathbf {F} \cdot {\frac {\partial f}{\partial \mathbf {p} }}=\left({\frac {\partial f}{\partial t}}\right)_{\mathrm {coll} }}$

In this context, F(r, t) is the force field acting on the particles in the fluid, and m is the mass of the particles. The term on the right hand side is added to describe the effect of collisions between particles; if it is zero then the particles do not collide. The collisionless Boltzmann equation, where individual collisions are replaced with long-range aggregated interactions, e.g. Coulomb interactions, is often called the Vlasov equation.

This equation is more useful than the principal one above, yet still incomplete, since f cannot be solved unless the collision term in f is known. This term cannot be found as easily or generally as the others – it is a statistical term representing the particle collisions, and requires knowledge of the statistics the particles obey, like the Maxwell–Boltzmann, Fermi–Dirac or Bose–Einstein distributions.

The collision term (Stosszahlansatz) and molecular chaos

Two-body collision term

A key insight applied by Boltzmann was to determine the collision term resulting solely from two-body collisions between particles that are assumed to be uncorrelated prior to the collision. This assumption was referred to by Boltzmann as the "Stosszahlansatz" and is also known as the "molecular chaos assumption". Under this assumption the collision term can be written as a momentum-space integral over the product of one-particle distribution functions:

${\displaystyle \left({\frac {\partial f}{\partial t}}\right)_{\text{coll}}=\iint gI(g,\Omega )[f(\mathbf {r} ,\mathbf {p'} _{A},t)f(\mathbf {r} ,\mathbf {p'} _{B},t)-f(\mathbf {r} ,\mathbf {p} _{A},t)f(\mathbf {r} ,\mathbf {p} _{B},t)]\,d\Omega \,d^{3}\mathbf {p} _{A}\,d^{3}\mathbf {p} _{B},}$

where p_A and p_B are the momenta of any two particles (labeled as A and B for convenience) before a collision, p′_A and p′_B are the momenta after the collision,

${\displaystyle g=|\mathbf {p} _{B}-\mathbf {p} _{A}|=|\mathbf {p'} _{B}-\mathbf {p'} _{A}|}$

is the magnitude of the relative momenta (see relative velocity for more on this concept), and I(g, Ω) is the differential cross section of the collision, in which the relative momenta of the colliding particles turns through an angle θ into the element of the solid angle dΩ, due to the collision.

Simplifications to the collision term

Since much of the challenge in solving the Boltzmann equation originates with the complex collision term, attempts have been made to "model" and simplify the collision term. The best known model equation is due to Bhatnagar, Gross and Krook. The assumption in the BGK approximation is that the effect of molecular collisions is to force a non-equilibrium distribution function at a point in physical space back to a Maxwellian equilibrium distribution function and that the rate at which this occurs is proportional to the molecular collision frequency. The Boltzmann equation is therefore modified to the BGK form:

${\displaystyle {\frac {\partial f}{\partial t}}+{\frac {\mathbf {p} }{m}}\cdot \nabla f+\mathbf {F} \cdot {\frac {\partial f}{\partial \mathbf {p} }}=\nu (f_{0}-f),}$

where ${\displaystyle \nu }$ is the molecular collision frequency, and ${\displaystyle f_{0}}$ is the local Maxwellian distribution function given the gas temperature at this point in space.

General equation (for a mixture)

For a mixture of chemical species labelled by indices i = 1, 2, 3, ..., n the equation for species i is

${\displaystyle {\frac {\partial f_{i}}{\partial t}}+{\frac {\mathbf {p} _{i}}{m_{i}}}\cdot \nabla f_{i}+\mathbf {F} \cdot {\frac {\partial f_{i}}{\partial \mathbf {p} _{i}}}=\left({\frac {\partial f_{i}}{\partial t}}\right)_{\text{coll}},}$

where f_i = f_i(r, p_i, t), and the collision term is

${\displaystyle \left({\frac {\partial f_{i}}{\partial t}}\right)_{\mathrm {coll} }=\sum _{j=1}^{n}\iint g_{ij}I_{ij}(g_{ij},\Omega )[f'_{i}f'_{j}-f_{i}f_{j}]\,d\Omega \,d^{3}\mathbf {p'} ,}$

where f′ = f′(p′_i, t), the magnitude of the relative momenta is

${\displaystyle g_{ij}=|\mathbf {p} _{i}-\mathbf {p} _{j}|=|\mathbf {p'} _{i}-\mathbf {p'} _{j}|,}$

and I_ij is the differential cross-section, as before, between particles i and j. The integration is over the momentum components in the integrand (which are labelled i and j). The sum of integrals describes the entry and exit of particles of species i in or out of the phase-space element.

Applications and extensions

Conservation equations

The Boltzmann equation can be used to derive the fluid dynamic conservation laws for mass, charge, momentum, and energy. For a fluid consisting of only one kind of particle, the number density n is given by

${\displaystyle n=\int f\,d^{3}p.}$

The average value of any function A is

${\displaystyle \langle A\rangle ={\frac {1}{n}}\int Af\,d^{3}p.}$

Since the conservation equations involve tensors, the Einstein summation convention will be used where repeated indices in a product indicate summation over those indices. Thus ${\displaystyle \mathbf {x} \mapsto x_{i}}$ and ${\displaystyle \mathbf {p} \mapsto p_{i}=mw_{i}}$, where ${\displaystyle w_{i}}$ is the particle velocity vector. Define ${\displaystyle A(p_{i})}$ as some function of momentum ${\displaystyle p_{i}}$ only, which is conserved in a collision. Assume also that the force ${\displaystyle F_{i}}$ is a function of position only, and that f is zero for ${\displaystyle p_{i}\to \pm \infty }$. Multiplying the Boltzmann equation by A and integrating over momentum yields four terms, which, using integration by parts, can be expressed as

${\displaystyle \int A{\frac {\partial f}{\partial t}}\,d^{3}p={\frac {\partial }{\partial t}}(n\langle A\rangle ),}$

${\displaystyle \int {\frac {p_{j}A}{m}}{\frac {\partial f}{\partial x_{j}}}\,d^{3}p={\frac {1}{m}}{\frac {\partial }{\partial x_{j}}}(n\langle Ap_{j}\rangle ),}$

${\displaystyle \int AF_{j}{\frac {\partial f}{\partial p_{j}}}\,d^{3}p=-nF_{j}\left\langle {\frac {\partial A}{\partial p_{j}}}\right\rangle ,}$

${\displaystyle \int A\left({\frac {\partial f}{\partial t}}\right)_{\text{coll}}\,d^{3}p=0,}$

where the last term is zero, since A is conserved in a collision. Letting ${\displaystyle A=m}$, the mass of the particle, the integrated Boltzmann equation becomes the conservation of mass equation:

${\displaystyle {\frac {\partial }{\partial t}}\rho +{\frac {\partial }{\partial x_{j}}}(\rho V_{j})=0,}$

where ${\displaystyle \rho =mn}$ is the mass density, and ${\displaystyle V_{i}=\langle w_{i}\rangle }$ is the average fluid velocity.

Letting ${\displaystyle A=p_{i}}$, the momentum of the particle, the integrated Boltzmann equation becomes the conservation of momentum equation:

${\displaystyle {\frac {\partial }{\partial t}}(\rho V_{i})+{\frac {\partial }{\partial x_{j}}}(\rho V_{i}V_{j}+P_{ij})-nF_{i}=0,}$

where ${\displaystyle P_{ij}=\rho \langle (w_{i}-V_{i})(w_{j}-V_{j})\rangle }$ is the pressure tensor (the viscous stress tensor plus the hydrostatic pressure).

Letting ${\displaystyle A={\frac {p_{i}p_{i}}{2m}}}$, the kinetic energy of the particle, the integrated Boltzmann equation becomes the conservation of energy equation:

${\displaystyle {\frac {\partial }{\partial t}}(u+{\tfrac {1}{2}}\rho V_{i}V_{i})+{\frac {\partial }{\partial x_{j}}}(uV_{j}+{\tfrac {1}{2}}\rho V_{i}V_{i}V_{j}+J_{qj}+P_{ij}V_{i})-nF_{i}V_{i}=0,}$

where ${\displaystyle u={\tfrac {1}{2}}\rho \langle (w_{i}-V_{i})(w_{i}-V_{i})\rangle }$ is the kinetic thermal energy density, and ${\displaystyle J_{qi}={\tfrac {1}{2}}\rho \langle (w_{i}-V_{i})(w_{k}-V_{k})(w_{k}-V_{k})\rangle }$ is the heat flux vector.

Hamiltonian mechanics

In Hamiltonian mechanics, the Boltzmann equation is often written more generally as

${\displaystyle {\hat {\mathbf {L} }}[f]=\mathbf {C} [f],\,}$

where L is the Liouville operator (there is an inconsistent definition between the Liouville operator as defined here and the one in the article linked) describing the evolution of a phase space volume and C is the collision operator. The non-relativistic form of L is

${\displaystyle {\hat {\mathbf {L} }}_{\mathrm {NR} }={\frac {\partial }{\partial t}}+{\frac {\mathbf {p} }{m}}\cdot \nabla +\mathbf {F} \cdot {\frac {\partial }{\partial \mathbf {p} }}\,.}$

Quantum theory and violation of particle number conservation

It is possible to write down relativistic quantum Boltzmann equations for relativistic quantum systems in which the number of particles is not conserved in collisions. This has several applications in physical cosmology, including the formation of the light elements in Big Bang nucleosynthesis, the production of dark matter and baryogenesis. It is not a priori clear that the state of a quantum system can be characterized by a classical phase space density f. However, for a wide class of applications a well-defined generalization of f exists which is the solution of an effective Boltzmann equation that can be derived from first principles of quantum field theory.

General relativity and astronomy

The Boltzmann equation is of use in galactic dynamics. A galaxy, under certain assumptions, may be approximated as a continuous fluid; its mass distribution is then represented by f; in galaxies, physical collisions between the stars are very rare, and the effect of gravitational collisions can be neglected for times far longer than the age of the universe.

Its generalization in general relativity is

${\displaystyle {\hat {\mathbf {L} }}_{\mathrm {GR} }=p^{\alpha }{\frac {\partial }{\partial x^{\alpha }}}-\Gamma ^{\alpha }{}_{\beta \gamma }p^{\beta }p^{\gamma }{\frac {\partial }{\partial p^{\alpha }}},}$

where Γ^α_βγ is the Christoffel symbol of the second kind (this assumes there are no external forces, so that particles move along geodesics in the absence of collisions), with the important subtlety that the density is a function in mixed contravariant-covariant (xⁱ, p_i) phase space as opposed to fully contravariant (xⁱ, pⁱ) phase space.

In physical cosmology the fully covariant approach has been used to study the cosmic microwave background radiation. More generically the study of processes in the early universe often attempt to take into account the effects of quantum mechanics and general relativity. In the very dense medium formed by the primordial plasma after the Big Bang, particles are continuously created and annihilated. In such an environment quantum coherence and the spatial extension of the wavefunction can affect the dynamics, making it questionable whether the classical phase space distribution f that appears in the Boltzmann equation is suitable to describe the system. In many cases it is, however, possible to derive an effective Boltzmann equation for a generalized distribution function from first principles of quantum field theory. This includes the formation of the light elements in Big Bang nucleosynthesis, the production of dark matter and baryogenesis.

Solving the equation

Exact solutions to the Boltzmann equations have been proven to exist in some cases; this analytical approach provides insight, but is not generally usable in practical problems.

Instead, numerical methods (including finite elements) are generally used to find approximate solutions to the various forms of the Boltzmann equation. Example applications range from hypersonic aerodynamics in rarefied gas flows to plasma flows.

Close to local equilibrium, solution of the Boltzmann equation can be represented by an asymptotic expansion in powers of Knudsen number (the Chapman-Enskog expansion). The first two terms of this expansion give the Euler equations and the Navier-Stokes equations. The higher terms have singularities. The problem of developing mathematically the limiting processes, which lead from the atomistic view (represented by Boltzmann's equation) to the laws of motion of continua, is an important part of Hilbert's sixth problem.

Atomic theory

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Atomic_theory 

 

This article is about the historical models of the atom. For a history of the study of how atoms combine to form molecules, see history of molecular theory. For the modern view of the atom which developed from atomic theory, see atomic physics.

The current theoretical model of the atom involves a dense nucleus surrounded by a probabilistic "cloud" of electrons

Atomic theory is the scientific theory that matter is composed of particles called atoms. Atomic theory traces its origins to an ancient philosophical tradition known as atomism. According to this idea, if one were to take a lump of matter and cut it into ever smaller pieces, one would reach a point where the pieces could not be further cut into anything smaller. Ancient Greek philosophers called these hypothetical ultimate particles of matter atomos, a word which meant "uncut".

In the early 1800s, the scientist John Dalton noticed that chemical substances seemed to combine and break down into other substances by weight in proportions that indicated that matter is indeed made of atoms as the ancient philosophers suspected. Shortly after 1850, certain physicists developed the kinetic theory of gases and of heat, which mathematically modelled the behavior of gases by assuming that gases are made of particles. In the early 20th century, Albert Einstein and Jean Perrin proved that Brownian motion (the erratic motion of pollen grains in water) is caused by the action of water molecules — this third line of evidence silenced remaining doubts among scientists as to whether atoms and molecules are real. Throughout the nineteenth century, some scientists had cautioned that the evidence for atoms was indirect, and therefore atoms might not actually be real, but only seem to be real.

By the early 20th century, scientists had developed fairly detailed and precise models for the structure of matter, which led to more rigorously-defined classifications for the tiny invisible particles that make up ordinary matter. An atom is now defined as the basic particle that composes a chemical element. Around the turn of the 20th century, physicists discovered that the particles that chemists called "atoms" are in fact agglomerations of even smaller particles (subatomic particles), but scientists kept the name out of convention. The term elementary particle is now used to refer to particles that are actually indivisible.

History

Philosophical atomism

The idea that matter is made up of discrete units is a very old idea, appearing in many ancient cultures such as Greece and India. The word "atom" (Greek: ἄτομος; atomos), meaning "uncuttable", was coined by the Pre-Socratic Greek philosophers Leucippus and his pupil Democritus (c.460–c.370 BC).

 Democritus taught that atoms were infinite in number, uncreated, and eternal, and that the qualities of an object result from the kind of atoms that compose it. Democritus's atomism was refined and elaborated by the later Greek philosopher Epicurus (341–270 BC), and by the Roman Epicurean poet Lucretius (c.99–c.55 BC). During the Early Middle Ages, atomism was mostly forgotten in western Europe.During the 12th century, atomism became known again in western Europe through references to it in the newly-rediscovered writings of Aristotle.

In the 14th century, the rediscovery of major works describing atomist teachings, including Lucretius's De rerum natura and Diogenes Laërtius's Lives and Opinions of Eminent Philosophers, led to increased scholarly attention on the subject. Nonetheless, because atomism was associated with the philosophy of Epicureanism, which contradicted orthodox Christian teachings, belief in atoms was not considered acceptable by most European philosophers. The French Catholic priest Pierre Gassendi (1592–1655) revived Epicurean atomism with modifications, arguing that atoms were created by God and, though extremely numerous, are not infinite and the first person who use term "molecule" to describe aggregate of atom. Gassendi's modified theory of atoms was popularized in France by the physician François Bernier (1620–1688) and in England by the natural philosopher Walter Charleton (1619–1707). The chemist Robert Boyle (1627–1691) and the physicist Isaac Newton (1642–1727) both defended atomism and, by the end of the 17th century, it had become accepted by portions of the scientific community.

John Dalton

Near the end of the 18th century, two laws about chemical reactions emerged without referring to the notion of an atomic theory. The first was the law of conservation of mass, closely associated with the work of Antoine Lavoisier, which states that the total mass in a chemical reaction remains constant (that is, the reactants have the same mass as the products). The second was the law of definite proportions. First established by the French chemist Joseph Proust in 1797 this law states that if a compound is broken down into its constituent chemical elements, then the masses of the constituents will always have the same proportions by weight, regardless of the quantity or source of the original substance.

John Dalton studied and expanded upon this previous work and defended a new idea, later known as the law of multiple proportions: if the same two elements can be combined to form a number of different compounds, then the ratios of the masses of the two elements in their various compounds will be represented by small whole numbers. This is a common pattern in chemical reactions that was observed by Dalton and other chemists at the time.

Example 1 — tin oxides: Dalton identified two oxides of tin. One is a grey powder in which for every 100 parts of tin there is 13.5 parts of oxygen. The other oxide is a white powder in which for every 100 parts of tin there is 27 parts of oxygen. 13.5 and 27 form a ratio of 1:2. These oxides are today known as tin(II) oxide (SnO) and tin(IV) oxide (SnO₂) respectively.

Example 2 — iron oxides: Dalton identified two oxides of iron. One is a black powder in which for every 100 parts of iron there is about 28 parts of oxygen. The other is a red powder in which for every 100 parts of iron there is 42 parts of oxygen. 28 and 42 form a ratio of 2:3. These oxides are today known as iron(II) oxide (better known as wüstite) and iron(III) oxide (the major constituent of rust). Their formulas are FeO and Fe₂O₃ respectively.

Example 3 — nitrogen oxides: There are three oxides of nitrogen in which for every 140 g of nitrogen, there is 80 g, 160 g, and 320 g of oxygen respectively, which gives a ratio of 1:2:4. These are nitrous oxide (N₂O), nitric oxide (NO), and nitrogen dioxide (NO₂) respectively.

This recurring pattern suggested that chemicals do not react in any arbitrary quantity, but in multiples of some basic indivisible unit of mass.

In his writings, Dalton used the term "atom" to refer to the basic particle of any chemical substance, not strictly for elements as is the practice today. Dalton did not use the word "molecule"; instead, he used the terms "compound atom" and "elementary atom".

Dalton believed atomic theory could also explain why water absorbed different gases in different proportions—for example, he found that water absorbed carbon dioxide far better than it absorbed nitrogen. Dalton hypothesized this was due to the differences in mass and complexity of the gases' respective particles. Indeed, carbon dioxide molecules (CO₂) are heavier and larger than nitrogen molecules (N₂).

Dalton proposed that each chemical element is composed of atoms of a single, unique type, and though they cannot be altered or destroyed by chemical means, they can combine to form more complex structures (chemical compounds). This marked the first truly scientific theory of the atom, since Dalton reached his conclusions by experimentation and examination of the results in an empirical fashion.

Various atoms and molecules as depicted in John Dalton's A New System of Chemical Philosophy (1808).

In 1803 Dalton orally presented his first list of relative atomic weights for a number of substances. This paper was published in 1805, but he did not discuss there exactly how he obtained these figures. The method was first revealed in 1807 by his acquaintance Thomas Thomson, in the third edition of Thomson's textbook, A System of Chemistry. Finally, Dalton published a full account in his own textbook, A New System of Chemical Philosophy, 1808 and 1810.

Dalton estimated the atomic weights according to the mass ratios in which they combined, with the hydrogen atom taken as unity. However, Dalton did not conceive that with some elements atoms exist in molecules—e.g. pure oxygen exists as O₂. He also mistakenly believed that the simplest compound between any two elements is always one atom of each (so he thought water was HO, not H₂O). This, in addition to the crudity of his equipment, flawed his results. For instance, in 1803 he believed that oxygen atoms were 5.5 times heavier than hydrogen atoms, because in water he measured 5.5 grams of oxygen for every 1 gram of hydrogen and believed the formula for water was HO. Adopting better data, in 1806 he concluded that the atomic weight of oxygen must actually be 7 rather than 5.5, and he retained this weight for the rest of his life. Others at this time had already concluded that the oxygen atom must weigh 8 relative to hydrogen equals 1, if one assumes Dalton's formula for the water molecule (HO), or 16 if one assumes the modern water formula (H₂O).

Avogadro

The flaw in Dalton's theory was corrected in principle in 1811 by Amedeo Avogadro. Avogadro had proposed that equal volumes of any two gases, at equal temperature and pressure, contain equal numbers of molecules (in other words, the mass of a gas's particles does not affect the volume that it occupies). Avogadro's law allowed him to deduce the diatomic nature of numerous gases by studying the volumes at which they reacted. For instance: since two liters of hydrogen will react with just one liter of oxygen to produce two liters of water vapor (at constant pressure and temperature), it meant a single oxygen molecule splits in two in order to form two particles of water. Thus, Avogadro was able to offer more accurate estimates of the atomic mass of oxygen and various other elements, and made a clear distinction between molecules and atoms.

Brownian Motion

In 1827, the British botanist Robert Brown observed that dust particles inside pollen grains floating in water constantly jiggled about for no apparent reason. In 1905, Albert Einstein theorized that this Brownian motion was caused by the water molecules continuously knocking the grains about, and developed a hypothetical mathematical model to describe it. This model was validated experimentally in 1908 by French physicist Jean Perrin, thus providing additional validation for particle theory (and by extension atomic theory).

Discovery of subatomic particles

The cathode rays (blue) were emitted from the cathode, sharpened to a beam by the slits, then deflected as they passed between the two electrified plates.

Atoms were thought to be the smallest possible division of matter until 1897 when J. J. Thomson discovered the electron through his work on cathode rays.

A Crookes tube is a sealed glass container in which two electrodes are separated by a vacuum. When a voltage is applied across the electrodes, cathode rays are generated, creating a glowing patch where they strike the glass at the opposite end of the tube. Through experimentation, Thomson discovered that the rays could be deflected by an electric field (in addition to magnetic fields, which was already known). He concluded that these rays, rather than being a form of light, were composed of very light negatively charged particles he called "corpuscles" (they would later be renamed electrons by other scientists). He measured the mass-to-charge ratio and discovered it was 1800 times smaller than that of hydrogen, the smallest atom. These corpuscles were a particle unlike any other previously known.

Thomson suggested that atoms were divisible, and that the corpuscles were their building blocks. To explain the overall neutral charge of the atom, he proposed that the corpuscles were distributed in a uniform sea of positive charge; this was the plum pudding model as the electrons were embedded in the positive charge like raisins in a plum pudding (although in Thomson's model they were not stationary).

Discovery of the nucleus

The Geiger–Marsden experiment
Left: Expected results: alpha particles passing through the plum pudding model of the atom with negligible deflection.
Right: Observed results: a small portion of the particles were deflected by the concentrated positive charge of the nucleus.

Thomson's plum pudding model was disproved in 1909 by one of his former students, Ernest Rutherford, who discovered that most of the mass and positive charge of an atom is concentrated in a very small fraction of its volume, which he assumed to be at the very center.

Ernest Rutherford and his colleagues Hans Geiger and Ernest Marsden came to have doubts about the Thomson model after they encountered difficulties when they tried to build an instrument to measure the charge-to-mass ratio of alpha particles (these are positively-charged particles emitted by certain radioactive substances such as radium). The alpha particles were being scattered by the air in the detection chamber, which made the measurements unreliable. Thomson had encountered a similar problem in his work on cathode rays, which he solved by creating a near-perfect vacuum in his instruments. Rutherford didn't think he'd run into this same problem because alpha particles are much heavier than electrons. According to Thomson's model of the atom, the positive charge in the atom is not concentrated enough to produce an electric field strong enough to deflect an alpha particle, and the electrons are so lightweight they should be pushed aside effortlessly by the much heavier alpha particles. Yet there was scattering, so Rutherford and his colleagues decided to investigate this scattering carefully.

Between 1908 and 1913, Rutheford and his colleagues performed a series of experiments in which they bombarded thin foils of metal with alpha particles. They spotted alpha particles being deflected by angles greater than 90°. To explain this, Rutherford proposed that the positive charge of the atom is not distributed throughout the atom's volume as Thomson believed, but is concentrated in a tiny nucleus at the center. Only such an intense concentration of charge could produce an electric field strong enough to deflect the alpha particles as observed.

First steps toward a quantum physical model of the atom

The planetary model of the atom had two significant shortcomings. The first is that, unlike planets orbiting a sun, electrons are charged particles. An accelerating electric charge is known to emit electromagnetic waves according to the Larmor formula in classical electromagnetism. An orbiting charge should steadily lose energy and spiral toward the nucleus, colliding with it in a small fraction of a second. The second problem was that the planetary model could not explain the highly peaked emission and absorption spectra of atoms that were observed.

The Bohr model of the atom

Quantum theory revolutionized physics at the beginning of the 20th century, when Max Planck and Albert Einstein postulated that light energy is emitted or absorbed in discrete amounts known as quanta (singular, quantum). In 1913, Niels Bohr incorporated this idea into his Bohr model of the atom, in which an electron could only orbit the nucleus in particular circular orbits with fixed angular momentum and energy, its distance from the nucleus (i.e., their radii) being proportional to its energy. Under this model an electron could not spiral into the nucleus because it could not lose energy in a continuous manner; instead, it could only make instantaneous "quantum leaps" between the fixed energy levels. When this occurred, light was emitted or absorbed at a frequency proportional to the change in energy (hence the absorption and emission of light in discrete spectra).

Bohr's model was not perfect. It could only predict the spectral lines of hydrogen; it couldn't predict those of multielectron atoms. Worse still, as spectrographic technology improved, additional spectral lines in hydrogen were observed which Bohr's model couldn't explain. In 1916, Arnold Sommerfeld added elliptical orbits to the Bohr model to explain the extra emission lines, but this made the model very difficult to use, and it still couldn't explain more complex atoms.

Discovery of isotopes

While experimenting with the products of radioactive decay, in 1913 radiochemist Frederick Soddy discovered that there appeared to be more than one element at each position on the periodic table. The term isotope was coined by Margaret Todd as a suitable name for these elements.

That same year, J. J. Thomson conducted an experiment in which he channeled a stream of neon ions through magnetic and electric fields, striking a photographic plate at the other end. He observed two glowing patches on the plate, which suggested two different deflection trajectories. Thomson concluded this was because some of the neon ions had a different mass. The nature of this differing mass would later be explained by the discovery of neutrons in 1932.

Discovery of nuclear particles

In 1917 Rutherford bombarded nitrogen gas with alpha particles and observed hydrogen nuclei being emitted from the gas (Rutherford recognized these, because he had previously obtained them bombarding hydrogen with alpha particles, and observing hydrogen nuclei in the products). Rutherford concluded that the hydrogen nuclei emerged from the nuclei of the nitrogen atoms themselves (in effect, he had split a nitrogen).

From his own work and the work of his students Bohr and Henry Moseley, Rutherford knew that the positive charge of any atom could always be equated to that of an integer number of hydrogen nuclei. This, coupled with the atomic mass of many elements being roughly equivalent to an integer number of hydrogen atoms - then assumed to be the lightest particles - led him to conclude that hydrogen nuclei were singular particles and a basic constituent of all atomic nuclei. He named such particles protons. Further experimentation by Rutherford found that the nuclear mass of most atoms exceeded that of the protons it possessed; he speculated that this surplus mass was composed of previously-unknown neutrally charged particles, which were tentatively dubbed "neutrons".

In 1928, Walter Bothe observed that beryllium emitted a highly penetrating, electrically neutral radiation when bombarded with alpha particles. It was later discovered that this radiation could knock hydrogen atoms out of paraffin wax. Initially it was thought to be high-energy gamma radiation, since gamma radiation had a similar effect on electrons in metals, but James Chadwick found that the ionization effect was too strong for it to be due to electromagnetic radiation, so long as energy and momentum were conserved in the interaction. In 1932, Chadwick exposed various elements, such as hydrogen and nitrogen, to the mysterious "beryllium radiation", and by measuring the energies of the recoiling charged particles, he deduced that the radiation was actually composed of electrically neutral particles which could not be massless like the gamma ray, but instead were required to have a mass similar to that of a proton. Chadwick now claimed these particles as Rutherford's neutrons. For his discovery of the neutron, Chadwick received the Nobel Prize in 1935.

Quantum physical models of the atom

The five filled atomic orbitals of a neon atom separated and arranged in order of increasing energy from left to right, with the last three orbitals being equal in energy. Each orbital holds up to two electrons, which most probably exist in the zones represented by the colored bubbles. Each electron is equally present in both orbital zones, shown here by color only to highlight the different wave phase.

In 1924, Louis de Broglie proposed that all moving particles—particularly subatomic particles such as electrons—exhibit a degree of wave-like behavior. Erwin Schrödinger, fascinated by this idea, explored whether or not the movement of an electron in an atom could be better explained as a wave rather than as a particle. Schrödinger's equation, published in 1926, describes an electron as a wave function instead of as a point particle. This approach elegantly predicted many of the spectral phenomena that Bohr's model failed to explain. Although this concept was mathematically convenient, it was difficult to visualize, and faced opposition. One of its critics, Max Born, proposed instead that Schrödinger's wave function described not the electron but rather all its possible states, and thus could be used to calculate the probability of finding an electron at any given location around the nucleus. This reconciled the two opposing theories of particle versus wave electrons and the idea of wave–particle duality was introduced. This theory stated that the electron may exhibit the properties of both a wave and a particle. For example, it can be refracted like a wave, and has mass like a particle.

A consequence of describing electrons as waveforms is that it is mathematically impossible to simultaneously derive the position and momentum of an electron. This became known as the Heisenberg uncertainty principle after the theoretical physicist Werner Heisenberg, who first described it and published it in 1927. This invalidated Bohr's model, with its neat, clearly defined circular orbits. The modern model of the atom describes the positions of electrons in an atom in terms of probabilities. An electron can potentially be found at any distance from the nucleus, but, depending on its energy level, exists more frequently in certain regions around the nucleus than others; this pattern is referred to as its atomic orbital. The orbitals come in a variety of shapes-sphere, dumbbell, torus, etc.-with the nucleus in the middle.

History of quantum mechanics

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/History_of_quantum_mechanics 

 

10 influential figures in the history of quantum mechanics. Left to right:

Max Planck, Albert Einstein,
Niels Bohr, Louis de Broglie,
Max Born, Paul Dirac,
Werner Heisenberg, Wolfgang Pauli,
Erwin Schrödinger, Richard Feynman.

The history of quantum mechanics is a fundamental part of the history of modern physics. Quantum mechanics' history, as it interlaces with the history of quantum chemistry, began essentially with a number of different scientific discoveries: the 1838 discovery of cathode rays by Michael Faraday; the 1859–60 winter statement of the black-body radiation problem by Gustav Kirchhoff; the 1877 suggestion by Ludwig Boltzmann that the energy states of a physical system could be discrete; the discovery of the photoelectric effect by Heinrich Hertz in 1887; and the 1900 quantum hypothesis by Max Planck that any energy-radiating atomic system can theoretically be divided into a number of discrete "energy elements" ε (Greek letter epsilon) such that each of these energy elements is proportional to the frequency ν with which each of them individually radiate energy, as defined by the following formula:

${\displaystyle \varepsilon =h\nu \,}$

where h is a numerical value called Planck's constant.

Then, Albert Einstein in 1905, in order to explain the photoelectric effect previously reported by Heinrich Hertz in 1887, postulated consistently with Max Planck's quantum hypothesis that light itself is made of individual quantum particles, which in 1926 came to be called photons by Gilbert N. Lewis. The photoelectric effect was observed upon shining light of particular wavelengths on certain materials, such as metals, which caused electrons to be ejected from those materials only if the light quantum energy was greater than the work function of the metal's surface.

The phrase "quantum mechanics" was coined (in German, Quantenmechanik) by the group of physicists including Max Born, Werner Heisenberg, and Wolfgang Pauli, at the University of Göttingen in the early 1920s, and was first used in Born's 1924 paper "Zur Quantenmechanik". In the years to follow, this theoretical basis slowly began to be applied to chemical structure, reactivity, and bonding.

Overview

Ludwig Boltzmann's diagram of the I₂ molecule proposed in 1898 showing the atomic "sensitive region" (α, β) of overlap.

Ludwig Boltzmann suggested in 1877 that the energy levels of a physical system, such as a molecule, could be discrete (as opposed to continuous). He was a founder of the Austrian Mathematical Society, together with the mathematicians Gustav von Escherich and Emil Müller. Boltzmann's rationale for the presence of discrete energy levels in molecules such as those of iodine gas had its origins in his statistical thermodynamics and statistical mechanics theories and was backed up by mathematical arguments, as would also be the case twenty years later with the first quantum theory put forward by Max Planck.

In 1900, the German physicist Max Planck reluctantly introduced the idea that energy is quantized in order to derive a formula for the observed frequency dependence of the energy emitted by a black body, called Planck's law, that included a Boltzmann distribution (applicable in the classical limit). Planck's law can be stated as follows: ${\displaystyle I(\nu ,T)={\frac {2h\nu ^{3}}{c^{2}}}{\frac {1}{e^{\frac {h\nu }{kT}}-1}},}$ where:

I(ν,T) is the energy per unit time (or the power) radiated per unit area of emitting surface in the normal direction per unit solid angle per unit frequency by a black body at temperature T;

h is the Planck constant;

c is the speed of light in a vacuum;

k is the Boltzmann constant;

ν (nu) is the frequency of the electromagnetic radiation; and

T is the temperature of the body in kelvins.

The earlier Wien approximation may be derived from Planck's law by assuming ${\displaystyle h\nu \gg kT}$.

Moreover, the application of Planck's quantum theory to the electron allowed Ștefan Procopiu in 1911–1913, and subsequently Niels Bohr in 1913, to calculate the magnetic moment of the electron, which was later called the "magneton;" similar quantum computations, but with numerically quite different values, were subsequently made possible for both the magnetic moments of the proton and the neutron that are three orders of magnitude smaller than that of the electron.

Photoelectric effect

The emission of electrons from a metal plate caused by light quanta (photons) with energy greater than the work function of the metal.

The photoelectric effect reported by Heinrich Hertz in 1887,

and explained by Albert Einstein in 1905.

Low-energy phenomena: Photoelectric effect

Mid-energy phenomena: Compton scattering

High-energy phenomena: Pair production

 

In 1905, Albert Einstein explained the photoelectric effect by postulating that light, or more generally all electromagnetic radiation, can be divided into a finite number of "energy quanta" that are localized points in space. From the introduction section of his March 1905 quantum paper, "On a heuristic viewpoint concerning the emission and transformation of light", Einstein states:

"According to the assumption to be contemplated here, when a light ray is spreading from a point, the energy is not distributed continuously over ever-increasing spaces, but consists of a finite number of 'energy quanta' that are localized in points in space, move without dividing, and can be absorbed or generated only as a whole."

This statement has been called the most revolutionary sentence written by a physicist of the twentieth century. These energy quanta later came to be called "photons", a term introduced by Gilbert N. Lewis in 1926. The idea that each photon had to consist of energy in terms of quanta was a remarkable achievement; it effectively solved the problem of black-body radiation attaining infinite energy, which occurred in theory if light were to be explained only in terms of waves. In 1913, Bohr explained the spectral lines of the hydrogen atom, again by using quantization, in his paper of July 1913 On the Constitution of Atoms and Molecules.

These theories, though successful, were strictly phenomenological: during this time, there was no rigorous justification for quantization, aside, perhaps, from Henri Poincaré's discussion of Planck's theory in his 1912 paper Sur la théorie des quanta. They are collectively known as the old quantum theory.

The phrase "quantum physics" was first used in Johnston's Planck's Universe in Light of Modern Physics (1931). 

 

With decreasing temperature, the peak of the blackbody radiation curve shifts to longer wavelengths and also has lower intensities. The blackbody radiation curves (1862) at left are also compared with the early, classical limit model of Rayleigh and Jeans (1900) shown at right. The short wavelength side of the curves was already approximated in 1896 by the Wien distribution law.

 

Niels Bohr's 1913 quantum model of the atom, which incorporated an explanation of Johannes Rydberg's 1888 formula, Max Planck's 1900 quantum hypothesis, i.e. that atomic energy radiators have discrete energy values (ε = hν), J. J. Thomson's 1904 plum pudding model, Albert Einstein's 1905 light quanta postulate, and Ernest Rutherford's 1907 discovery of the atomic nucleus. Note that the electron does not travel along the black line when emitting a photon. It jumps, disappearing from the outer orbit and appearing in the inner one and cannot exist in the space between orbits 2 and 3.

In 1923, the French physicist Louis de Broglie put forward his theory of matter waves by stating that particles can exhibit wave characteristics and vice versa. This theory was for a single particle and derived from special relativity theory. Building on de Broglie's approach, modern quantum mechanics was born in 1925, when the German physicists Werner Heisenberg, Max Born, and Pascual Jordandeveloped matrix mechanics and the Austrian physicist Erwin Schrödinger invented wave mechanics and the non-relativistic Schrödinger equation as an approximation of the generalised case of de Broglie's theory. Schrödinger subsequently showed that the two approaches were equivalent.

Heisenberg formulated his uncertainty principle in 1927, and the Copenhagen interpretation started to take shape at about the same time. Starting around 1927, Paul Dirac began the process of unifying quantum mechanics with special relativity by proposing the Dirac equation for the electron. The Dirac equation achieves the relativistic description of the wavefunction of an electron that Schrödinger failed to obtain. It predicts electron spin and led Dirac to predict the existence of the positron. He also pioneered the use of operator theory, including the influential bra–ket notation, as described in his famous 1930 textbook. During the same period, Hungarian polymath John von Neumann formulated the rigorous mathematical basis for quantum mechanics as the theory of linear operators on Hilbert spaces, as described in his likewise famous 1932 textbook. These, like many other works from the founding period, still stand, and remain widely used.

The field of quantum chemistry was pioneered by physicists Walter Heitler and Fritz London, who published a study of the covalent bond of the hydrogen molecule in 1927. Quantum chemistry was subsequently developed by a large number of workers, including the American theoretical chemist Linus Pauling at Caltech, and John C. Slater into various theories such as Molecular Orbital Theory or Valence Theory.

Beginning in 1927, researchers attempted to apply quantum mechanics to fields instead of single particles, resulting in quantum field theories. Early workers in this area include P.A.M. Dirac, W. Pauli, V. Weisskopf, and P. Jordan. This area of research culminated in the formulation of quantum electrodynamics by R.P. Feynman, F. Dyson, J. Schwinger, and S. Tomonaga during the 1940s. Quantum electrodynamics describes a quantum theory of electrons, positrons, and the electromagnetic field, and served as a model for subsequent quantum field theories.

Feynman diagram of gluon radiation in quantum chromodynamics

The theory of quantum chromodynamics was formulated beginning in the early 1960s. The theory as we know it today was formulated by Politzer, Gross and Wilczek in 1975.

Building on pioneering work by Schwinger, Higgs and Goldstone, the physicists Glashow, Weinberg and Salam independently showed how the weak nuclear force and quantum electrodynamics could be merged into a single electroweak force, for which they received the 1979 Nobel Prize in Physics.

Founding experiments

• Thomas Young's double-slit experiment demonstrating the wave nature of light. (c. 1801)
• Henri Becquerel discovers radioactivity. (1896)
• J. J. Thomson's cathode ray tube experiments (discovers the electron and its negative charge). (1897)
• The study of black-body radiation between 1850 and 1900, which could not be explained without quantum concepts.
• The photoelectric effect: Einstein explained this in 1905 (and later received a Nobel prize for it) using the concept of photons, particles of light with quantized energy.
• Robert Millikan's oil-drop experiment, which showed that electric charge occurs as quanta (whole units). (1909)
• Ernest Rutherford's gold foil experiment disproved the plum pudding model of the atom which suggested that the mass and positive charge of the atom are almost uniformly distributed. This led to the planetary model of the atom (1911).
• James Franck and Gustav Hertz's electron collision experiment shows that energy absorption by mercury atoms is quantized. (1914)
• Otto Stern and Walther Gerlach conduct the Stern–Gerlach experiment, which demonstrates the quantized nature of particle spin. (1920)
• Clinton Davisson and Lester Germer demonstrate the wave nature of the electron^[10] in the Electron diffraction experiment. (1927)
• Clyde L. Cowan and Frederick Reines confirm the existence of the neutrino in the neutrino experiment. (1955)
• Clauss Jönsson's double-slit experiment with electrons. (1961)
• The Quantum Hall effect, discovered in 1980 by Klaus von Klitzing. The quantized version of the Hall effect has allowed for the definition of a new practical standard for electrical resistance and for an extremely precise independent determination of the fine structure constant.
• The experimental verification of quantum entanglement by John Clauser and Stuart Freedman. (1972)
• The Mach–Zehnder interferometer experiment conducted by Paul Kwiat, Harold Wienfurter, Thomas Herzog, Anton Zeilinger, and Mark Kasevich, providing experimental verification of the Elitzur–Vaidman bomb tester, proving interaction-free measurement is possible. (1994)