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Old quantum theory

The old quantum theory is a collection of results from the years 1900–1925[1] which predate modern quantum mechanics. The theory was never complete or self-consistent, but was instead a set of heuristic corrections to classical mechanics.[2] The theory has come to be understood as the semi-classical approximation[3] to modern quantum mechanics.[4] The main and final accomplishments of the old quantum theory were the determination of the modern form of the periodic table by Edmund Stoner and the Pauli exclusion principle which were both premised on the Arnold Sommerfeld enhancements to the Bohr model of the atom.[5][6]

The main tool of the old quantum theory was the Bohr–Sommerfeld quantization condition, a procedure for selection of certain allowed states of a classical system: the system can then only exist in one of the allowed states and not in any other state.

History edit

The old quantum theory was instigated by the 1900 work of Max Planck on the emission and absorption of light in a black body with his discovery of Planck’s law introducing his quantum of action, and began in earnest after the work of Albert Einstein on the specific heats of solids in 1907 brought him to the attention of Walther Nernst.[7] Einstein, followed by Debye, applied quantum principles to the motion of atoms, explaining the specific heat anomaly.

In 1910, Arthur Erich Haas develops J. J. Thomson’s atomic model in his 1910 paper[8] that outlined a treatment of the hydrogen atom involving quantization of electronic orbitals, thus anticipating the Bohr model (1913) by three years.

John William Nicholson is noted as the first to create an atomic model that quantized angular momentum as h/2π.[9][10] Niels Bohr quoted him in his 1913 paper of the Bohr model of the atom.[11]

In 1913, Niels Bohr displayed rudiments of the later defined correspondence principle and used it to formulate a model of the hydrogen atom which explained the line spectrum. In the next few years Arnold Sommerfeld extended the quantum rule to arbitrary integrable systems making use of the principle of adiabatic invariance of the quantum numbers introduced by Lorentz and Einstein. Sommerfeld made a crucial contribution[12] by quantizing the z-component of the angular momentum, which in the old quantum era was called "space quantization" (German: Richtungsquantelung). This model, which became known as the Bohr–Sommerfeld model, allowed the orbits of the electron to be ellipses instead of circles, and introduced the concept of quantum degeneracy. The theory would have correctly explained the Zeeman effect, except for the issue of electron spin. Sommerfeld's model was much closer to the modern quantum mechanical picture than Bohr's.

Throughout the 1910s and well into the 1920s, many problems were attacked using the old quantum theory with mixed results. Molecular rotation and vibration spectra were understood and the electron's spin was discovered, leading to the confusion of half-integer quantum numbers. Max Planck introduced the zero point energy and Arnold Sommerfeld semiclassically quantized the relativistic hydrogen atom. Hendrik Kramers explained the Stark effect. Bose and Einstein gave the correct quantum statistics for photons.

 
The Sommerfeld extensions of the 1913 solar system Bohr model of the hydrogen atom showing the addition of elliptical orbits to explain spectral fine structure. The circular n=3 corresponds to a higher energy orbital.[13] n=3 has multiple orbits because of azimuthal quantum number.

Kramers gave a prescription for calculating transition probabilities between quantum states in terms of Fourier components of the motion, ideas which were extended in collaboration with Werner Heisenberg to a semiclassical matrix-like description of atomic transition probabilities. Heisenberg went on to reformulate all of quantum theory in terms of a version of these transition matrices, creating matrix mechanics.

In 1924, Louis de Broglie introduced the wave theory of matter, which was extended to a semiclassical equation for matter waves by Albert Einstein a short time later. In 1926 Erwin Schrödinger found a completely quantum mechanical wave-equation, which reproduced all the successes of the old quantum theory without ambiguities and inconsistencies. Schrödinger's wave mechanics developed separately from matrix mechanics until Schrödinger and others proved that the two methods predicted the same experimental consequences. Paul Dirac later proved in 1926 that both methods can be obtained from a more general method called transformation theory.

In the 1950s Joseph Keller updated Bohr–Sommerfeld quantization using Einstein's interpretation of 1917,[14] now known as Einstein–Brillouin–Keller method. In 1971, Martin Gutzwiller took into account that this method only works for integrable systems and derived a semiclassical way of quantizing chaotic systems from path integrals.[15]

Basic principles edit

The basic idea of the old quantum theory is that the motion in an atomic system is quantized, or discrete. The system obeys classical mechanics except that not every motion is allowed, only those motions which obey the quantization condition:

 

where the   are the momenta of the system and the   are the corresponding coordinates. The quantum numbers   are integers and the integral is taken over one period of the motion at constant energy (as described by the Hamiltonian). The integral is an area in phase space, which is a quantity called the action and is quantized in units of the (unreduced) Planck constant. For this reason, the Planck constant was often called the quantum of action.

In order for the old quantum condition to make sense, the classical motion must be separable, meaning that there are separate coordinates   in terms of which the motion is periodic. The periods of the different motions do not have to be the same, they can even be incommensurate, but there must be a set of coordinates where the motion decomposes in a multi-periodic way.

The motivation for the old quantum condition was the correspondence principle, complemented by the physical observation that the quantities which are quantized must be adiabatic invariants. Given Planck's quantization rule for the harmonic oscillator, either condition determines the correct classical quantity to quantize in a general system up to an additive constant.

This quantization condition is often known as the Wilson–Sommerfeld rule,[16] proposed independently by William Wilson[17] and Arnold Sommerfeld.[18]

Examples edit

Thermal properties of the harmonic oscillator edit

The simplest system in the old quantum theory is the harmonic oscillator, whose Hamiltonian is:

 

The old quantum theory yields a recipe for the quantization of the energy levels of the harmonic oscillator, which, when combined with the Boltzmann probability distribution of thermodynamics, yields the correct expression for the stored energy and specific heat of a quantum oscillator both at low and at ordinary temperatures. Applied as a model for the specific heat of solids, this resolved a discrepancy in pre-quantum thermodynamics that had troubled 19th-century scientists. Let us now describe this.

The level sets of H are the orbits, and the quantum condition is that the area enclosed by an orbit in phase space is an integer. It follows that the energy is quantized according to the Planck rule:

 

a result which was known well before, and used to formulate the old quantum condition. This result differs by   from the results found with the help of quantum mechanics. This constant is neglected in the derivation of the old quantum theory, and its value cannot be determined using it.

The thermal properties of a quantized oscillator may be found by averaging the energy in each of the discrete states assuming that they are occupied with a Boltzmann weight:

 

kT is Boltzmann constant times the absolute temperature, which is the temperature as measured in more natural units of energy. The quantity   is more fundamental in thermodynamics than the temperature, because it is the thermodynamic potential associated to the energy.

From this expression, it is easy to see that for large values of  , for very low temperatures, the average energy U in the Harmonic oscillator approaches zero very quickly, exponentially fast. The reason is that kT is the typical energy of random motion at temperature T, and when this is smaller than  , there is not enough energy to give the oscillator even one quantum of energy. So the oscillator stays in its ground state, storing next to no energy at all.

This means that at very cold temperatures, the change in energy with respect to beta, or equivalently the change in energy with respect to temperature, is also exponentially small. The change in energy with respect to temperature is the specific heat, so the specific heat is exponentially small at low temperatures, going to zero like

 

At small values of  , at high temperatures, the average energy U is equal to  . This reproduces the equipartition theorem of classical thermodynamics: every harmonic oscillator at temperature T has energy kT on average. This means that the specific heat of an oscillator is constant in classical mechanics and equal to k. For a collection of atoms connected by springs, a reasonable model of a solid, the total specific heat is equal to the total number of oscillators times k. There are overall three oscillators for each atom, corresponding to the three possible directions of independent oscillations in three dimensions. So the specific heat of a classical solid is always 3k per atom, or in chemistry units, 3R per mole of atoms.

Monatomic solids at room temperatures have approximately the same specific heat of 3k per atom, but at low temperatures they don't. The specific heat is smaller at colder temperatures, and it goes to zero at absolute zero. This is true for all material systems, and this observation is called the third law of thermodynamics. Classical mechanics cannot explain the third law, because in classical mechanics the specific heat is independent of the temperature.

This contradiction between classical mechanics and the specific heat of cold materials was noted by James Clerk Maxwell in the 19th century, and remained a deep puzzle for those who advocated an atomic theory of matter. Einstein resolved this problem in 1906 by proposing that atomic motion is quantized. This was the first application of quantum theory to mechanical systems. A short while later, Peter Debye gave a quantitative theory of solid specific heats in terms of quantized oscillators with various frequencies (see Einstein solid and Debye model).

One-dimensional potential: U = 0 edit

One-dimensional problems are easy to solve. At any energy E, the value of the momentum p is found from the conservation equation:

 

which is integrated over all values of q between the classical turning points, the places where the momentum vanishes. The integral is easiest for a particle in a box of length L, where the quantum condition is:

 

which gives the allowed momenta:

 

and the energy levels

 

One-dimensional potential: U = Fx edit

Another easy case to solve with the old quantum theory is a linear potential on the positive halfline, the constant confining force F binding a particle to an impenetrable wall. This case is much more difficult in the full quantum mechanical treatment, and unlike the other examples, the semiclassical answer here is not exact but approximate, becoming more accurate at large quantum numbers.

 

so that the quantum condition is

 

which determines the energy levels,

 

In the specific case F=mg, the particle is confined by the gravitational potential of the earth and the "wall" here is the surface of the earth.

One-dimensional potential: U = 12kx2 edit

This case is also easy to solve, and the semiclassical answer here agrees with the quantum one to within the ground-state energy. Its quantization-condition integral is

 

with solution

 

for oscillation angular frequency  , as before.

Rotator edit

Another simple system is the rotator. A rotator consists of a mass M at the end of a massless rigid rod of length R and in two dimensions has the Lagrangian:

 

which determines that the angular momentum J conjugate to  , the polar angle,  . The old quantum condition requires that J multiplied by the period of   is an integer multiple of the Planck constant:

 

the angular momentum to be an integer multiple of  . In the Bohr model, this restriction imposed on circular orbits was enough to determine the energy levels.

In three dimensions, a rigid rotator can be described by two angles —   and  , where   is the inclination relative to an arbitrarily chosen z-axis while   is the rotator angle in the projection to the xy plane. The kinetic energy is again the only contribution to the Lagrangian:

 

And the conjugate momenta are   and  . The equation of motion for   is trivial:   is a constant:

 

which is the z-component of the angular momentum. The quantum condition demands that the integral of the constant   as   varies from 0 to   is an integer multiple of h:

 

And m is called the magnetic quantum number, because the z component of the angular momentum is the magnetic moment of the rotator along the z direction in the case where the particle at the end of the rotator is charged.

Since the three-dimensional rotator is rotating about an axis, the total angular momentum should be restricted in the same way as the two-dimensional rotator. The two quantum conditions restrict the total angular momentum and the z-component of the angular momentum to be the integers l,m. This condition is reproduced in modern quantum mechanics, but in the era of the old quantum theory it led to a paradox: how can the orientation of the angular momentum relative to the arbitrarily chosen z-axis be quantized? This seems to pick out a direction in space.

This phenomenon, the quantization of angular momentum about an axis, was given the name space quantization, because it seemed incompatible with rotational invariance. In modern quantum mechanics, the angular momentum is quantized the same way, but the discrete states of definite angular momentum in any one orientation are quantum superpositions of the states in other orientations, so that the process of quantization does not pick out a preferred axis. For this reason, the name "space quantization" fell out of favor, and the same phenomenon is now called the quantization of angular momentum.

Hydrogen atom edit

The angular part of the hydrogen atom is just the rotator, and gives the quantum numbers l and m. The only remaining variable is the radial coordinate, which executes a periodic one-dimensional potential motion, which can be solved.

For a fixed value of the total angular momentum L, the Hamiltonian for a classical Kepler problem is (the unit of mass and unit of energy redefined to absorb two constants):

 

Fixing the energy to be (a negative) constant and solving for the radial momentum  , the quantum condition integral is:

 

which can be solved with the method of residues,[12] and gives a new quantum number   which determines the energy in combination with  . The energy is:

 

and it only depends on the sum of k and l, which is the principal quantum number n. Since k is positive, the allowed values of l for any given n are no bigger than n. The energies reproduce those in the Bohr model, except with the correct quantum mechanical multiplicities, with some ambiguity at the extreme values.

De Broglie waves edit

In 1905, Einstein noted that the entropy of the quantized electromagnetic field oscillators in a box is, for short wavelength, equal to the entropy of a gas of point particles in the same box. The number of point particles is equal to the number of quanta. Einstein concluded that the quanta could be treated as if they were localizable objects (see[19] page 139/140), particles of light. Today we call them photons (a name coined by Gilbert N. Lewis in a letter to Nature.[20][21][22])

Einstein's theoretical argument was based on thermodynamics, on counting the number of states, and so was not completely convincing. Nevertheless, he concluded that light had attributes of both waves and particles, more precisely that an electromagnetic standing wave with frequency   with the quantized energy:

 

should be thought of as consisting of n photons each with an energy  . Einstein could not describe how the photons were related to the wave.

The photons have momentum as well as energy, and the momentum had to be   where   is the wavenumber of the electromagnetic wave. This is required by relativity, because the momentum and energy form a four-vector, as do the frequency and wave-number.

In 1924, as a PhD candidate, Louis de Broglie proposed a new interpretation of the quantum condition. He suggested that all matter, electrons as well as photons, are described by waves obeying the relations.

 

or, expressed in terms of wavelength   instead,

 

He then noted that the quantum condition:

 

counts the change in phase for the wave as it travels along the classical orbit, and requires that it be an integer multiple of  . Expressed in wavelengths, the number of wavelengths along a classical orbit must be an integer. This is the condition for constructive interference, and it explained the reason for quantized orbits—the matter waves make standing waves only at discrete frequencies, at discrete energies.

For example, for a particle confined in a box, a standing wave must fit an integer number of wavelengths between twice the distance between the walls. The condition becomes:

 

so that the quantized momenta are:

 

reproducing the old quantum energy levels.

This development was given a more mathematical form by Einstein, who noted that the phase function for the waves,  , in a mechanical system should be identified with the solution to the Hamilton–Jacobi equation, an equation which William Rowan Hamilton believed to be a short-wavelength limit of a sort of wave mechanics in the 19th century. Schrödinger then found the proper wave equation which matched the Hamilton–Jacobi equation for the phase; this is now known as the Schrödinger equation.

Kramers transition matrix edit

The old quantum theory was formulated only for special mechanical systems which could be separated into action angle variables which were periodic. It did not deal with the emission and absorption of radiation. Nevertheless, Hendrik Kramers was able to find heuristics for describing how emission and absorption should be calculated.

Kramers suggested that the orbits of a quantum system should be Fourier analyzed, decomposed into harmonics at multiples of the orbit frequency:

 

The index n describes the quantum numbers of the orbit, it would be nlm in the Sommerfeld model. The frequency   is the angular frequency of the orbit   while k is an index for the Fourier mode. Bohr had suggested that the k-th harmonic of the classical motion correspond to the transition from level n to level nk.

Kramers proposed that the transition between states were analogous to classical emission of radiation, which happens at frequencies at multiples of the orbit frequencies. The rate of emission of radiation is proportional to  , as it would be in classical mechanics. The description was approximate, since the Fourier components did not have frequencies that exactly match the energy spacings between levels.

This idea led to the development of matrix mechanics.

Limitations edit

The old quantum theory had some limitations:[23]

  • The old quantum theory provides no means to calculate the intensities of the spectral lines.
  • It fails to explain the anomalous Zeeman effect (that is, where the spin of the electron cannot be neglected).
  • It cannot quantize "chaotic" systems, i.e. dynamical systems in which trajectories are neither closed nor periodic and whose analytical form does not exist. This presents a problem for systems as simple as a 2-electron atom which is classically chaotic analogously to the famous gravitational three-body problem.

However it can be used to describe atoms with more than one electron (e.g. Helium) and the Zeeman effect.[24] It was later proposed that the old quantum theory is in fact the semi-classical approximation to the canonical quantum mechanics[25] but its limitations are still under investigation.

See also edit

References edit

  1. ^ Pais, Abraham (2005). Subtle is the Lord: The Science and the Life of Albert Einstein (illustrated ed.). OUP Oxford. p. 28. ISBN 978-0-19-280672-7. Extract of page 28
  2. ^ ter Haar, D. (1967). The Old Quantum Theory. Pergamon Press. pp. 206. ISBN 978-0-08-012101-7.
  3. ^ Semi-classical approximation. Encyclopedia of Mathematics. URL: https://www.encyclopediaofmath.org/index.php?title=Semi-classical_approximation
  4. ^ Sakurai, Napolitano (2014). "Quantum Dynamics". Modern Quantum Mechanics. Pearson. ISBN 978-1-292-02410-3.
  5. ^ Kragh, Helge (1979). "Niels Bohr's Second Atomic Theory". Historical Studies in the Physical Sciences. 10: 123–186. doi:10.2307/27757389. JSTOR 27757389.
  6. ^ Kumar, Manjit. Quantum: Einstein, Bohr, and the great debate about the nature of reality / Manjit Kumar.—1st American ed., 2008. Chap.7.
  7. ^ Thomas Kuhn, Black-Body Theory and the Quantum Discontinuity, 1894–1912 (Chicago: University of Chicago Press, 1978)
  8. ^
    • Haas, Arthur Erich (1910) "Über die elektrodynamische Bedeutung des Planck'schen Strahlungsgesetzes und über eine neue Bestimmung des elektrischen Elementarquantums und der Dimension des Wasserstoffatoms". Sitzungsberichte der kaiserlichen Akademie der Wissenschaften in Wien. Abt 2A, (119) pp 119-144.
    • Haas A.E. Die Entwicklungsgeschichte des Satzes von der Erhaltung der Kraft. Habilitation Thesis, Vienna, 1909.
    • Hermann, A. Arthur Erich Haas, Der erste Quantenansatz für das Atom. Stuttgart, 1965 [contains a reprint].
  9. ^
    • Nicholson, J. W. (1911). "The Spectrum of Nebulium". Monthly Notices of the Royal Astronomical Society. 72: 49–64. doi:10.1093/mnras/72.1.49.
    • Nicholson, J. W. (1911). "The Constitution of the Solar Corona. I.: Protofluorine". Monthly Notices of the Royal Astronomical Society. 72 (2): 139–150. doi:10.1093/mnras/72.2.139.
    • Nicholson, J. W. (1912). "The Constitution of the Solar Corona. IL". Monthly Notices of the Royal Astronomical Society. 72 (8): 677–693. doi:10.1093/mnras/72.8.677.
    • Nicholson, J. W. (1912). "On the New Nebular Line at 4353". Monthly Notices of the Royal Astronomical Society. 72 (8): 693. doi:10.1093/mnras/72.8.693.
    • Nicholson, J. W. (1912). "The Constitution of the Solar Corona. III". Monthly Notices of the Royal Astronomical Society. 72 (9): 729–740. doi:10.1093/mnras/72.9.729.
  10. ^ McCormmach, Russell (1966). "The Atomic Theory of John William Nicholson". Archive for History of Exact Sciences. 3 (2): 160–184. doi:10.1007/BF00357268. JSTOR 41133258. S2CID 120797894.
  11. ^ Bohr, N. (1913). "On the constitution of atoms and molecules". The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. Series 6. 26 (151): 1–25. Bibcode:1913PMag...26....1B. doi:10.1080/14786441308634955.
  12. ^ a b Sommerfeld, Arnold (1919). Atombau und Spektrallinien'. Braunschweig: Friedrich Vieweg und Sohn. ISBN 978-3-87144-484-5.
  13. ^ https://www.dumdummotijheelcollege.ac.in/pdf/1586768332.pdf. {{cite web}}: Missing or empty |title= (help)
  14. ^ The Collected Papers of Albert Einstein, vol. 6, A. Engel, trans., Princeton U. Press, Princeton, NJ (1997), p. 434
  15. ^ Stone, A.D. (August 2005). "Einstein's unknown insight and the problem of quantizing chaos" (PDF). Physics Today. 58 (8): 37–43. Bibcode:2005PhT....58h..37S. doi:10.1063/1.2062917.
  16. ^ Pauling, Linus; Wilson, Edgar Bright (2012). Introduction to quantum mechanics : with applications to chemistry. New York, N.Y.: Dover Publications. ISBN 9780486134932. OCLC 830473042.
  17. ^ Wilson, William (1915). "LXXXIII. The quantum-theory of radiation and line spectra". The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. 29 (174): 795–802. doi:10.1080/14786440608635362.
  18. ^ Sommerfeld, Arnold (1916). "Zur Quantentheorie der Spektrallinien". Annalen der Physik. 356 (17): 1–94. Bibcode:1916AnP...356....1S. doi:10.1002/andp.19163561702. ISSN 0003-3804.
  19. ^ Einstein, Albert (1905). "Über einen die Erzeugung und Verwandlung des Lichtes betreffenden heuristischen Gesichtspunkt" [On a Heuristic Point of View Concerning the Production and Transformation of Light] (PDF). Annalen der Physik (in German). 17 (6): 132–148. Bibcode:1905AnP...322..132E. doi:10.1002/andp.19053220607. Retrieved 2008-02-18.
  20. ^ "December 18, 1926: Gilbert Lewis coins "photon" in letter to Nature". www.aps.org. Retrieved 2019-03-09.
  21. ^ "Gilbert N. Lewis". Atomic Heritage Foundation. Retrieved 2019-03-09.
  22. ^ Kragh, Helge (2014). "Photon: New light on an old name". arXiv:1401.0293 [physics.hist-ph].
  23. ^ Chaddha, G.S. (2006). Quantum Mechanics. New Delhi: New Age international. pp. 8–9. ISBN 978-81-224-1465-3.
  24. ^ Solov’ev, E. A. (2011). "Classical approach in atomic physics". European Physical Journal D. 65 (3): 331–351. arXiv:1003.4387. Bibcode:2011EPJD...65..331S. doi:10.1140/epjd/e2011-20261-6. S2CID 119204790.
  25. ^ L.D. Landau, E.M. Lifshitz (1977). Quantum Mechanics: Non-Relativistic Theory. Vol. 3 (3rd ed.). Pergamon Press. ISBN 978-0-08-020940-1.

Further reading edit

  • Thewlis, J., ed. (1962). Encyclopaedic Dictionary of Physics.
  • Pais, Abraham (1982). "Max Born's Statistical Interpretation of Quantum Mechanics" (PDF). Science. 218 (4578): 1193–8. Bibcode:1982Sci...218.1193P. doi:10.1126/science.218.4578.1193. PMID 17802457. S2CID 34406257. Address to annual meeting of the Optical Society of America October 21, 1982 (Tucson AZ). Retrieved 2013-09-08.
  • Planck, Max (1922). The origin and development of the quantum theory. Translated by Silberstein, L.; Clarke, H. T. Oxford: Clarendon Press.

quantum, theory, quantum, theory, collection, results, from, years, 1900, 1925, which, predate, modern, quantum, mechanics, theory, never, complete, self, consistent, instead, heuristic, corrections, classical, mechanics, theory, come, understood, semi, classi. The old quantum theory is a collection of results from the years 1900 1925 1 which predate modern quantum mechanics The theory was never complete or self consistent but was instead a set of heuristic corrections to classical mechanics 2 The theory has come to be understood as the semi classical approximation 3 to modern quantum mechanics 4 The main and final accomplishments of the old quantum theory were the determination of the modern form of the periodic table by Edmund Stoner and the Pauli exclusion principle which were both premised on the Arnold Sommerfeld enhancements to the Bohr model of the atom 5 6 The main tool of the old quantum theory was the Bohr Sommerfeld quantization condition a procedure for selection of certain allowed states of a classical system the system can then only exist in one of the allowed states and not in any other state Contents 1 History 2 Basic principles 3 Examples 3 1 Thermal properties of the harmonic oscillator 3 2 One dimensional potential U 0 3 3 One dimensional potential U Fx 3 4 One dimensional potential U 1 2 kx2 3 5 Rotator 3 6 Hydrogen atom 4 De Broglie waves 5 Kramers transition matrix 6 Limitations 7 See also 8 References 9 Further readingHistory editThe old quantum theory was instigated by the 1900 work of Max Planck on the emission and absorption of light in a black body with his discovery of Planck s law introducing his quantum of action and began in earnest after the work of Albert Einstein on the specific heats of solids in 1907 brought him to the attention of Walther Nernst 7 Einstein followed by Debye applied quantum principles to the motion of atoms explaining the specific heat anomaly In 1910 Arthur Erich Haas develops J J Thomson s atomic model in his 1910 paper 8 that outlined a treatment of the hydrogen atom involving quantization of electronic orbitals thus anticipating the Bohr model 1913 by three years John William Nicholson is noted as the first to create an atomic model that quantized angular momentum as h 2p 9 10 Niels Bohr quoted him in his 1913 paper of the Bohr model of the atom 11 In 1913 Niels Bohr displayed rudiments of the later defined correspondence principle and used it to formulate a model of the hydrogen atom which explained the line spectrum In the next few years Arnold Sommerfeld extended the quantum rule to arbitrary integrable systems making use of the principle of adiabatic invariance of the quantum numbers introduced by Lorentz and Einstein Sommerfeld made a crucial contribution 12 by quantizing the z component of the angular momentum which in the old quantum era was called space quantization German Richtungsquantelung This model which became known as the Bohr Sommerfeld model allowed the orbits of the electron to be ellipses instead of circles and introduced the concept of quantum degeneracy The theory would have correctly explained the Zeeman effect except for the issue of electron spin Sommerfeld s model was much closer to the modern quantum mechanical picture than Bohr s Throughout the 1910s and well into the 1920s many problems were attacked using the old quantum theory with mixed results Molecular rotation and vibration spectra were understood and the electron s spin was discovered leading to the confusion of half integer quantum numbers Max Planck introduced the zero point energy and Arnold Sommerfeld semiclassically quantized the relativistic hydrogen atom Hendrik Kramers explained the Stark effect Bose and Einstein gave the correct quantum statistics for photons nbsp The Sommerfeld extensions of the 1913 solar system Bohr model of the hydrogen atom showing the addition of elliptical orbits to explain spectral fine structure The circular n 3 corresponds to a higher energy orbital 13 n 3 has multiple orbits because of azimuthal quantum number Kramers gave a prescription for calculating transition probabilities between quantum states in terms of Fourier components of the motion ideas which were extended in collaboration with Werner Heisenberg to a semiclassical matrix like description of atomic transition probabilities Heisenberg went on to reformulate all of quantum theory in terms of a version of these transition matrices creating matrix mechanics In 1924 Louis de Broglie introduced the wave theory of matter which was extended to a semiclassical equation for matter waves by Albert Einstein a short time later In 1926 Erwin Schrodinger found a completely quantum mechanical wave equation which reproduced all the successes of the old quantum theory without ambiguities and inconsistencies Schrodinger s wave mechanics developed separately from matrix mechanics until Schrodinger and others proved that the two methods predicted the same experimental consequences Paul Dirac later proved in 1926 that both methods can be obtained from a more general method called transformation theory In the 1950s Joseph Keller updated Bohr Sommerfeld quantization using Einstein s interpretation of 1917 14 now known as Einstein Brillouin Keller method In 1971 Martin Gutzwiller took into account that this method only works for integrable systems and derived a semiclassical way of quantizing chaotic systems from path integrals 15 Basic principles editSee also Jun Ishiwara Quantum physics The basic idea of the old quantum theory is that the motion in an atomic system is quantized or discrete The system obeys classical mechanics except that not every motion is allowed only those motions which obey the quantization condition H p q E p i d q i n i h displaystyle oint H p q E p i dq i n i h nbsp where the p i displaystyle p i nbsp are the momenta of the system and the q i displaystyle q i nbsp are the corresponding coordinates The quantum numbers n i displaystyle n i nbsp are integers and the integral is taken over one period of the motion at constant energy as described by the Hamiltonian The integral is an area in phase space which is a quantity called the action and is quantized in units of the unreduced Planck constant For this reason the Planck constant was often called the quantum of action In order for the old quantum condition to make sense the classical motion must be separable meaning that there are separate coordinates q i displaystyle q i nbsp in terms of which the motion is periodic The periods of the different motions do not have to be the same they can even be incommensurate but there must be a set of coordinates where the motion decomposes in a multi periodic way The motivation for the old quantum condition was the correspondence principle complemented by the physical observation that the quantities which are quantized must be adiabatic invariants Given Planck s quantization rule for the harmonic oscillator either condition determines the correct classical quantity to quantize in a general system up to an additive constant This quantization condition is often known as the Wilson Sommerfeld rule 16 proposed independently by William Wilson 17 and Arnold Sommerfeld 18 Examples editThermal properties of the harmonic oscillator edit The simplest system in the old quantum theory is the harmonic oscillator whose Hamiltonian is H p 2 2 m m w 2 q 2 2 displaystyle H p 2 over 2m m omega 2 q 2 over 2 nbsp The old quantum theory yields a recipe for the quantization of the energy levels of the harmonic oscillator which when combined with the Boltzmann probability distribution of thermodynamics yields the correct expression for the stored energy and specific heat of a quantum oscillator both at low and at ordinary temperatures Applied as a model for the specific heat of solids this resolved a discrepancy in pre quantum thermodynamics that had troubled 19th century scientists Let us now describe this The level sets of H are the orbits and the quantum condition is that the area enclosed by an orbit in phase space is an integer It follows that the energy is quantized according to the Planck rule E n ℏ w displaystyle E n hbar omega nbsp a result which was known well before and used to formulate the old quantum condition This result differs by 1 2 ℏ w displaystyle tfrac 1 2 hbar omega nbsp from the results found with the help of quantum mechanics This constant is neglected in the derivation of the old quantum theory and its value cannot be determined using it The thermal properties of a quantized oscillator may be found by averaging the energy in each of the discrete states assuming that they are occupied with a Boltzmann weight U n ℏ w n e b n ℏ w n e b n ℏ w ℏ w e b ℏ w 1 e b ℏ w w h e r e b 1 k T displaystyle U sum n hbar omega ne beta n hbar omega over sum n e beta n hbar omega hbar omega e beta hbar omega over 1 e beta hbar omega rm where beta frac 1 kT nbsp kT is Boltzmann constant times the absolute temperature which is the temperature as measured in more natural units of energy The quantity b displaystyle beta nbsp is more fundamental in thermodynamics than the temperature because it is the thermodynamic potential associated to the energy From this expression it is easy to see that for large values of b displaystyle beta nbsp for very low temperatures the average energy U in the Harmonic oscillator approaches zero very quickly exponentially fast The reason is that kT is the typical energy of random motion at temperature T and when this is smaller than ℏ w displaystyle hbar omega nbsp there is not enough energy to give the oscillator even one quantum of energy So the oscillator stays in its ground state storing next to no energy at all This means that at very cold temperatures the change in energy with respect to beta or equivalently the change in energy with respect to temperature is also exponentially small The change in energy with respect to temperature is the specific heat so the specific heat is exponentially small at low temperatures going to zero like exp ℏ w k T displaystyle exp hbar omega kT nbsp dd At small values of b displaystyle beta nbsp at high temperatures the average energy U is equal to 1 b k T displaystyle 1 beta kT nbsp This reproduces the equipartition theorem of classical thermodynamics every harmonic oscillator at temperature T has energy kT on average This means that the specific heat of an oscillator is constant in classical mechanics and equal to k For a collection of atoms connected by springs a reasonable model of a solid the total specific heat is equal to the total number of oscillators times k There are overall three oscillators for each atom corresponding to the three possible directions of independent oscillations in three dimensions So the specific heat of a classical solid is always 3k per atom or in chemistry units 3R per mole of atoms Monatomic solids at room temperatures have approximately the same specific heat of 3k per atom but at low temperatures they don t The specific heat is smaller at colder temperatures and it goes to zero at absolute zero This is true for all material systems and this observation is called the third law of thermodynamics Classical mechanics cannot explain the third law because in classical mechanics the specific heat is independent of the temperature This contradiction between classical mechanics and the specific heat of cold materials was noted by James Clerk Maxwell in the 19th century and remained a deep puzzle for those who advocated an atomic theory of matter Einstein resolved this problem in 1906 by proposing that atomic motion is quantized This was the first application of quantum theory to mechanical systems A short while later Peter Debye gave a quantitative theory of solid specific heats in terms of quantized oscillators with various frequencies see Einstein solid and Debye model One dimensional potential U 0 edit One dimensional problems are easy to solve At any energy E the value of the momentum p is found from the conservation equation 2 m E U q 2 m E p const displaystyle sqrt 2m E U q sqrt 2mE p text const nbsp which is integrated over all values of q between the classical turning points the places where the momentum vanishes The integral is easiest for a particle in a box of length L where the quantum condition is 2 0 L p d q n h displaystyle 2 int 0 L p dq nh nbsp which gives the allowed momenta p n h 2 L displaystyle p nh over 2L nbsp and the energy levels E n p 2 2 m n 2 h 2 8 m L 2 displaystyle E n p 2 over 2m n 2 h 2 over 8mL 2 nbsp One dimensional potential U Fx edit Another easy case to solve with the old quantum theory is a linear potential on the positive halfline the constant confining force F binding a particle to an impenetrable wall This case is much more difficult in the full quantum mechanical treatment and unlike the other examples the semiclassical answer here is not exact but approximate becoming more accurate at large quantum numbers 2 0 E F 2 m E F x d x n h displaystyle 2 int 0 frac E F sqrt 2m E Fx dx nh nbsp so that the quantum condition is 4 3 2 m E 3 2 F n h displaystyle 4 over 3 sqrt 2m E 3 2 over F nh nbsp which determines the energy levels E n 3 n h F 4 2 m 2 3 displaystyle E n left 3nhF over 4 sqrt 2m right 2 3 nbsp In the specific case F mg the particle is confined by the gravitational potential of the earth and the wall here is the surface of the earth One dimensional potential U 1 2 kx2 edit This case is also easy to solve and the semiclassical answer here agrees with the quantum one to within the ground state energy Its quantization condition integral is 2 2 E k 2 E k 2 m E 1 2 k x 2 d x n h displaystyle 2 int sqrt frac 2E k sqrt frac 2E k sqrt 2m left E frac 1 2 kx 2 right dx nh nbsp with solution E n h 2 p k m n ℏ w displaystyle E n frac h 2 pi sqrt frac k m n hbar omega nbsp for oscillation angular frequency w displaystyle omega nbsp as before Rotator edit Another simple system is the rotator A rotator consists of a mass M at the end of a massless rigid rod of length R and in two dimensions has the Lagrangian L M R 2 2 8 2 displaystyle L MR 2 over 2 dot theta 2 nbsp which determines that the angular momentum J conjugate to 8 displaystyle theta nbsp the polar angle J M R 2 8 displaystyle J MR 2 dot theta nbsp The old quantum condition requires that J multiplied by the period of 8 displaystyle theta nbsp is an integer multiple of the Planck constant 2 p J n h displaystyle 2 pi J nh nbsp the angular momentum to be an integer multiple of ℏ displaystyle hbar nbsp In the Bohr model this restriction imposed on circular orbits was enough to determine the energy levels In three dimensions a rigid rotator can be described by two angles 8 displaystyle theta nbsp and ϕ displaystyle phi nbsp where 8 displaystyle theta nbsp is the inclination relative to an arbitrarily chosen z axis while ϕ displaystyle phi nbsp is the rotator angle in the projection to the x y plane The kinetic energy is again the only contribution to the Lagrangian L M R 2 2 8 2 M R 2 2 sin 8 ϕ 2 displaystyle L MR 2 over 2 dot theta 2 MR 2 over 2 sin theta dot phi 2 nbsp And the conjugate momenta are p 8 8 displaystyle p theta dot theta nbsp and p ϕ sin 8 2 ϕ displaystyle p phi sin theta 2 dot phi nbsp The equation of motion for ϕ displaystyle phi nbsp is trivial p ϕ displaystyle p phi nbsp is a constant p ϕ l ϕ displaystyle p phi l phi nbsp which is the z component of the angular momentum The quantum condition demands that the integral of the constant l ϕ displaystyle l phi nbsp as ϕ displaystyle phi nbsp varies from 0 to 2 p displaystyle 2 pi nbsp is an integer multiple of h l ϕ m ℏ displaystyle l phi m hbar nbsp And m is called the magnetic quantum number because the z component of the angular momentum is the magnetic moment of the rotator along the z direction in the case where the particle at the end of the rotator is charged Since the three dimensional rotator is rotating about an axis the total angular momentum should be restricted in the same way as the two dimensional rotator The two quantum conditions restrict the total angular momentum and the z component of the angular momentum to be the integers l m This condition is reproduced in modern quantum mechanics but in the era of the old quantum theory it led to a paradox how can the orientation of the angular momentum relative to the arbitrarily chosen z axis be quantized This seems to pick out a direction in space This phenomenon the quantization of angular momentum about an axis was given the name space quantization because it seemed incompatible with rotational invariance In modern quantum mechanics the angular momentum is quantized the same way but the discrete states of definite angular momentum in any one orientation are quantum superpositions of the states in other orientations so that the process of quantization does not pick out a preferred axis For this reason the name space quantization fell out of favor and the same phenomenon is now called the quantization of angular momentum Hydrogen atom edit The angular part of the hydrogen atom is just the rotator and gives the quantum numbers l and m The only remaining variable is the radial coordinate which executes a periodic one dimensional potential motion which can be solved For a fixed value of the total angular momentum L the Hamiltonian for a classical Kepler problem is the unit of mass and unit of energy redefined to absorb two constants H p r 2 2 l 2 2 r 2 1 r displaystyle H p r 2 over 2 l 2 over 2r 2 1 over r nbsp Fixing the energy to be a negative constant and solving for the radial momentum p r displaystyle p r nbsp the quantum condition integral is 2 E l 2 r 2 2 r d r k h displaystyle oint sqrt 2E l 2 over r 2 2 over r dr kh nbsp which can be solved with the method of residues 12 and gives a new quantum number k displaystyle k nbsp which determines the energy in combination with l displaystyle l nbsp The energy is E 1 2 k l 2 displaystyle E 1 over 2 k l 2 nbsp and it only depends on the sum of k and l which is the principal quantum number n Since k is positive the allowed values of l for any given n are no bigger than n The energies reproduce those in the Bohr model except with the correct quantum mechanical multiplicities with some ambiguity at the extreme values De Broglie waves editIn 1905 Einstein noted that the entropy of the quantized electromagnetic field oscillators in a box is for short wavelength equal to the entropy of a gas of point particles in the same box The number of point particles is equal to the number of quanta Einstein concluded that the quanta could be treated as if they were localizable objects see 19 page 139 140 particles of light Today we call them photons a name coined by Gilbert N Lewis in a letter to Nature 20 21 22 Einstein s theoretical argument was based on thermodynamics on counting the number of states and so was not completely convincing Nevertheless he concluded that light had attributes of both waves and particles more precisely that an electromagnetic standing wave with frequency w displaystyle omega nbsp with the quantized energy E n ℏ w displaystyle E n hbar omega nbsp should be thought of as consisting of n photons each with an energy ℏ w displaystyle hbar omega nbsp Einstein could not describe how the photons were related to the wave The photons have momentum as well as energy and the momentum had to be ℏ k displaystyle hbar k nbsp where k displaystyle k nbsp is the wavenumber of the electromagnetic wave This is required by relativity because the momentum and energy form a four vector as do the frequency and wave number In 1924 as a PhD candidate Louis de Broglie proposed a new interpretation of the quantum condition He suggested that all matter electrons as well as photons are described by waves obeying the relations p ℏ k displaystyle p hbar k nbsp or expressed in terms of wavelength l displaystyle lambda nbsp instead p h l displaystyle p h over lambda nbsp He then noted that the quantum condition p d x ℏ k d x 2 p ℏ n displaystyle int p dx hbar int k dx 2 pi hbar n nbsp counts the change in phase for the wave as it travels along the classical orbit and requires that it be an integer multiple of 2 p displaystyle 2 pi nbsp Expressed in wavelengths the number of wavelengths along a classical orbit must be an integer This is the condition for constructive interference and it explained the reason for quantized orbits the matter waves make standing waves only at discrete frequencies at discrete energies For example for a particle confined in a box a standing wave must fit an integer number of wavelengths between twice the distance between the walls The condition becomes n l 2 L displaystyle n lambda 2L nbsp so that the quantized momenta are p n h 2 L displaystyle p frac nh 2L nbsp reproducing the old quantum energy levels This development was given a more mathematical form by Einstein who noted that the phase function for the waves 8 J x displaystyle theta J x nbsp in a mechanical system should be identified with the solution to the Hamilton Jacobi equation an equation which William Rowan Hamilton believed to be a short wavelength limit of a sort of wave mechanics in the 19th century Schrodinger then found the proper wave equation which matched the Hamilton Jacobi equation for the phase this is now known as the Schrodinger equation Kramers transition matrix editThe old quantum theory was formulated only for special mechanical systems which could be separated into action angle variables which were periodic It did not deal with the emission and absorption of radiation Nevertheless Hendrik Kramers was able to find heuristics for describing how emission and absorption should be calculated Kramers suggested that the orbits of a quantum system should be Fourier analyzed decomposed into harmonics at multiples of the orbit frequency X n t k e i k w t X n k displaystyle X n t sum k infty infty e ik omega t X n k nbsp The index n describes the quantum numbers of the orbit it would be n l m in the Sommerfeld model The frequency w displaystyle omega nbsp is the angular frequency of the orbit 2 p T n displaystyle 2 pi T n nbsp while k is an index for the Fourier mode Bohr had suggested that the k th harmonic of the classical motion correspond to the transition from level n to level n k Kramers proposed that the transition between states were analogous to classical emission of radiation which happens at frequencies at multiples of the orbit frequencies The rate of emission of radiation is proportional to X k 2 displaystyle X k 2 nbsp as it would be in classical mechanics The description was approximate since the Fourier components did not have frequencies that exactly match the energy spacings between levels This idea led to the development of matrix mechanics Limitations editThe old quantum theory had some limitations 23 The old quantum theory provides no means to calculate the intensities of the spectral lines It fails to explain the anomalous Zeeman effect that is where the spin of the electron cannot be neglected It cannot quantize chaotic systems i e dynamical systems in which trajectories are neither closed nor periodic and whose analytical form does not exist This presents a problem for systems as simple as a 2 electron atom which is classically chaotic analogously to the famous gravitational three body problem However it can be used to describe atoms with more than one electron e g Helium and the Zeeman effect 24 It was later proposed that the old quantum theory is in fact the semi classical approximation to the canonical quantum mechanics 25 but its limitations are still under investigation See also editBohr model Bohr Sommerfeld model BKS theoryReferences edit Pais Abraham 2005 Subtle is the Lord The Science and the Life of Albert Einstein illustrated ed OUP Oxford p 28 ISBN 978 0 19 280672 7 Extract of page 28 ter Haar D 1967 The Old Quantum Theory Pergamon Press pp 206 ISBN 978 0 08 012101 7 Semi classical approximation Encyclopedia of Mathematics URL https www encyclopediaofmath org index php title Semi classical approximation Sakurai Napolitano 2014 Quantum Dynamics Modern Quantum Mechanics Pearson ISBN 978 1 292 02410 3 Kragh Helge 1979 Niels Bohr s Second Atomic Theory Historical Studies in the Physical Sciences 10 123 186 doi 10 2307 27757389 JSTOR 27757389 Kumar Manjit Quantum Einstein Bohr and the great debate about the nature of reality Manjit Kumar 1st American ed 2008 Chap 7 Thomas Kuhn Black Body Theory and the Quantum Discontinuity 1894 1912 Chicago University of Chicago Press 1978 Haas Arthur Erich 1910 Uber die elektrodynamische Bedeutung des Planck schen Strahlungsgesetzes und uber eine neue Bestimmung des elektrischen Elementarquantums und der Dimension des Wasserstoffatoms Sitzungsberichte der kaiserlichen Akademie der Wissenschaften in Wien Abt 2A 119 pp 119 144 Haas A E Die Entwicklungsgeschichte des Satzes von der Erhaltung der Kraft Habilitation Thesis Vienna 1909 Hermann A Arthur Erich Haas Der erste Quantenansatz fur das Atom Stuttgart 1965 contains a reprint Nicholson J W 1911 The Spectrum of Nebulium Monthly Notices of the Royal Astronomical Society 72 49 64 doi 10 1093 mnras 72 1 49 Nicholson J W 1911 The Constitution of the Solar Corona I Protofluorine Monthly Notices of the Royal Astronomical Society 72 2 139 150 doi 10 1093 mnras 72 2 139 Nicholson J W 1912 The Constitution of the Solar Corona IL Monthly Notices of the Royal Astronomical Society 72 8 677 693 doi 10 1093 mnras 72 8 677 Nicholson J W 1912 On the New Nebular Line at 4353 Monthly Notices of the Royal Astronomical Society 72 8 693 doi 10 1093 mnras 72 8 693 Nicholson J W 1912 The Constitution of the Solar Corona III Monthly Notices of the Royal Astronomical Society 72 9 729 740 doi 10 1093 mnras 72 9 729 McCormmach Russell 1966 The Atomic Theory of John William Nicholson Archive for History of Exact Sciences 3 2 160 184 doi 10 1007 BF00357268 JSTOR 41133258 S2CID 120797894 Bohr N 1913 On the constitution of atoms and molecules The London Edinburgh and Dublin Philosophical Magazine and Journal of Science Series 6 26 151 1 25 Bibcode 1913PMag 26 1B doi 10 1080 14786441308634955 a b Sommerfeld Arnold 1919 Atombau und Spektrallinien Braunschweig Friedrich Vieweg und Sohn ISBN 978 3 87144 484 5 https www dumdummotijheelcollege ac in pdf 1586768332 pdf a href Template Cite web html title Template Cite web cite web a Missing or empty title help The Collected Papers of Albert Einstein vol 6 A Engel trans Princeton U Press Princeton NJ 1997 p 434 Stone A D August 2005 Einstein s unknown insight and the problem of quantizing chaos PDF Physics Today 58 8 37 43 Bibcode 2005PhT 58h 37S doi 10 1063 1 2062917 Pauling Linus Wilson Edgar Bright 2012 Introduction to quantum mechanics with applications to chemistry New York N Y Dover Publications ISBN 9780486134932 OCLC 830473042 Wilson William 1915 LXXXIII The quantum theory of radiation and line spectra The London Edinburgh and Dublin Philosophical Magazine and Journal of Science 29 174 795 802 doi 10 1080 14786440608635362 Sommerfeld Arnold 1916 Zur Quantentheorie der Spektrallinien Annalen der Physik 356 17 1 94 Bibcode 1916AnP 356 1S doi 10 1002 andp 19163561702 ISSN 0003 3804 Einstein Albert 1905 Uber einen die Erzeugung und Verwandlung des Lichtes betreffenden heuristischen Gesichtspunkt On a Heuristic Point of View Concerning the Production and Transformation of Light PDF Annalen der Physik in German 17 6 132 148 Bibcode 1905AnP 322 132E doi 10 1002 andp 19053220607 Retrieved 2008 02 18 December 18 1926 Gilbert Lewis coins photon in letter to Nature www aps org Retrieved 2019 03 09 Gilbert N Lewis Atomic Heritage Foundation Retrieved 2019 03 09 Kragh Helge 2014 Photon New light on an old name arXiv 1401 0293 physics hist ph Chaddha G S 2006 Quantum Mechanics New Delhi New Age international pp 8 9 ISBN 978 81 224 1465 3 Solov ev E A 2011 Classical approach in atomic physics European Physical Journal D 65 3 331 351 arXiv 1003 4387 Bibcode 2011EPJD 65 331S doi 10 1140 epjd e2011 20261 6 S2CID 119204790 L D Landau E M Lifshitz 1977 Quantum Mechanics Non Relativistic Theory Vol 3 3rd ed Pergamon Press ISBN 978 0 08 020940 1 Further reading editThewlis J ed 1962 Encyclopaedic Dictionary of Physics Pais Abraham 1982 Max Born s Statistical Interpretation of Quantum Mechanics PDF Science 218 4578 1193 8 Bibcode 1982Sci 218 1193P doi 10 1126 science 218 4578 1193 PMID 17802457 S2CID 34406257 Address to annual meeting of the Optical Society of America October 21 1982 Tucson AZ Retrieved 2013 09 08 Planck Max 1922 The origin and development of the quantum theory Translated by Silberstein L Clarke H T Oxford Clarendon Press Retrieved from https en wikipedia org w index php title Old quantum theory amp oldid 1227062789, wikipedia, wiki, book, books, library,

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