It is hard to realise that the electron was only discovered a little over 100 years ago in 1897. That it was not expected is illustrated by a remark made by J J Thomson, the discoverer of the electron. He said
I was told long afterwards by a distinguished physicist who had been present at my lecture that he thought I had been pulling their leg.The neutron was not discovered until 1932 so it is against this background that we trace the beginnings of quantum theory back to 1859.
In 1859 Gustav Kirchhoff proved a theorem about blackbody radiation. A blackbody is an object that absorbs all the energy that falls upon it and, because it reflects no light, it would appear black to an observer. A blackbody is also a perfect emitter and Kirchhoff proved that the energy emitted E depends only on the temperature T and the frequency v of the emitted energy, i.e.
In 1879 Josef Stefan proposed, on experimental grounds, that the total energy emitted by a hot body was proportional to the fourth power of the temperature. In the generality stated by Stefan this is false. The same conclusion was reached in 1884 by Ludwig Boltzmann for blackbody radiation, this time from theoretical considerations using thermodynamics and Maxwell's electromagnetic theory. The result, now known as the Stefan-Boltzmann law, does not fully answer Kirchhoff's challenge since it does not answer the question for specific wavelengths.
In 1896 Wilhelm Wien proposed a solution to the Kirchhoff challenge. However although his solution matches experimental observations closely for small values of the wavelength, it was shown to break down in the far infrared by Rubens and Kurlbaum.
Kirchhoff, who had been at Heidelberg, moved to Berlin. Boltzmann was offered his chair in Heidelberg but turned it down. The chair was then offered to Hertz who also declined the offer, so it was offered again, this time to Planck and he accepted.
Rubens visited Planck in October 1900 and explained his results to him. Within a few hours of Rubens leaving Planck's house Planck had guessed the correct formula for Kirchhoff's J function. This guess fitted experimental evidence at all wavelengths very well but Planck was not satisfied with this and tried to give a theoretical derivation of the formula. To do this he made the unprecedented step of assuming that the total energy is made up of indistinguishable energy elements - quanta of energy. He wrote
Experience will prove whether this hypothesis is realised in naturePlanck himself gave credit to Boltzmann for his statistical method but Planck's approach was fundamentally different. However theory had now deviated from experiment and was based on a hypothesis with no experimental basis. Planck won the 1918 Nobel Prize for Physics for this work.
In 1901 Ricci and Levi-Civita published Absolute differential calculus. It had been Christoffel's discovery of 'covariant differentiation' in 1869 which let Ricci extend the theory of tensor analysis to Riemannian space of n dimensions. The Ricci and Levi-Civita definitions were thought to give the most general formulation of a tensor. This work was not done with quantum theory in mind but, as so often happens, the mathematics necessary to embody a physical theory had appeared at precisely the right moment.
In 1905 Einstein examined the photoelectric effect. The photoelectric effect is the release of electrons from certain metals or semiconductors by the action of light. The electromagnetic theory of light gives results at odds with experimental evidence. Einstein proposed a quantum theory of light to solve the difficulty and then he realised that Planck's theory made implicit use of the light quantum hypothesis. By 1906 Einstein had correctly guessed that energy changes occur in a quantum material oscillator in changes in jumps which are multiples of v where is Planck's reduced constant and v is the frequency. Einstein received the 1921 Nobel Prize for Physics, in 1922, for this work on the photoelectric effect.
In 1913 Niels Bohr wrote a revolutionary paper on the hydrogen atom. He discovered the major laws of the spectral lines. This work earned Bohr the 1922 Nobel Prize for Physics. Arthur Compton derived relativistic kinematics for the scattering of a photon (a light quantum) off an electron at rest in 1923.
However there were concepts in the new quantum theory which gave major worries to many leading physicists. Einstein, in particular, worried about the element of 'chance' which had entered physics. In fact Rutherford had introduced spontaneous effect when discussing radio-active decay in 1900. In 1924 Einstein wrote:-
There are therefore now two theories of light, both indispensable, and - as one must admit today despite twenty years of tremendous effort on the part of theoretical physicists - without any logical connection.In the same year, 1924, Bohr, Kramers and Slater made important theoretical proposals regarding the interaction of light and matter which rejected the photon. Although the proposals were the wrong way forward they stimulated important experimental work. Bohr addressed certain paradoxes in his work.
Up to this stage quantum theory was set up in Euclidean space and used Cartesian tensors of linear and angular momentum. However quantum theory was about to enter a new era.
The year 1924 saw the publication of another fundamental paper. It was written by Satyendra Nath Bose and rejected by a referee for publication. Bose then sent the manuscript to Einstein who immediately saw the importance of Bose's work and arranged for its publication. Bose proposed different states for the photon. He also proposed that there is no conservation of the number of photons. Instead of statistical independence of particles, Bose put particles into cells and talked about statistical independence of cells. Time has shown that Bose was right on all these points.
Work was going on at almost the same time as Bose's which was also of fundamental importance. The doctoral thesis of Louis de Broglie was presented which extended the particle-wave duality for light to all particles, in particular to electrons. Schrödinger in 1926 published a paper giving his equation for the hydrogen atom and heralded the birth of wave mechanics. Schrödinger introduced operators associated with each dynamical variable.
The year 1926 saw the complete solution of the derivation of Planck's law after 26 years. It was solved by Dirac. Also in 1926 Born abandoned the causality of traditional physics. Speaking of collisions Born wrote
One does not get an answer to the question, What is the state after collision? but only to the question, How probable is a given effect of the collision? From the standpoint of our quantum mechanics, there is no quantity which causally fixes the effect of a collision in an individual event.Heisenberg wrote his first paper on quantum mechanics in 1925 and 2 years later stated his uncertainty principle. It states that the process of measuring the position x of a particle disturbs the particle's momentum p, so that
the nonvalidity of rigorous causality is necessary and not just consistently possible.Heisenberg's work used matrix methods made possible by the work of Cayley on matrices 50 years earlier. In fact 'rival' matrix mechanics deriving from Heisenberg's work and wave mechanics resulting from Schrödinger's work now entered the arena. These were not properly shown to be equivalent until the necessary mathematics was developed by Riesz about 25 years later.
Also in 1927 Bohr stated that space-time coordinates and causality are complementary. Pauli realised that spin, one of the states proposed by Bose, corresponded to a new kind of tensor, one not covered by the Ricci and Levi-Civita work of 1901. However the mathematics of this had been anticipated by Eli Cartan who introduced a 'spinor' as part of a much more general investigation in 1913.
Dirac, in 1928, gave the first solution of the problem of expressing quantum theory in a form which was invariant under the Lorentz group of transformations of special relativity. He expressed d'Alembert's wave equation in terms of operator algebra.
The uncertainty principle was not accepted by everyone. Its most outspoken opponent was Einstein. He devised a challenge to Niels Bohr which he made at a conference which they both attended in 1930. Einstein suggested a box filled with radiation with a clock fitted in one side. The clock is designed to open a shutter and allow one photon to escape. Weigh the box again some time later and the photon energy and its time of escape can both be measured with arbitrary accuracy. Of course this is not meant to be an actual experiment, only a 'thought experiment'.
Niels Bohr is reported to have spent an unhappy evening, and Einstein a happy one, after this challenge by Einstein to the uncertainty principle. However Niels Bohr had the final triumph, for the next day he had the solution. The mass is measured by hanging a compensation weight under the box. This is turn imparts a momentum to the box and there is an error in measuring the position. Time, according to relativity, is not absolute and the error in the position of the box translates into an error in measuring the time.
Although Einstein was never happy with the uncertainty principle, he was forced, rather grudgingly, to accept it after Bohr's explanation.
In 1932 von Neumann put quantum theory on a firm theoretical basis. Some of the earlier work had lacked mathematical rigour, but von Neumann put the whole theory into the setting of operator algebra.
Article by: J J O'Connor and E F Robertson
MacTutor History of Mathematics