Quantum mechanics developed in two distinct phases. The first phase, known as the
old quantum theory, began around 1900 with radically new approaches to explanations physical phenomena not understood by classical mechanics of the 1800s.
Planck introduces quanta to explain black-body radiation Thermal radiation is electromagnetic radiation emitted from the surface of an object due to the object's internal energy. If an object is heated sufficiently, it starts to emit light at the red end of the visible
spectrum, as it becomes
red hot. Heating it further causes the color to change from red to yellow, white, and blue, as it emits light at increasingly shorter wavelengths (higher frequencies). A perfect emitter is also a perfect absorber: when it is cold, such an object looks perfectly black, because it absorbs all the light that falls on it and emits none. Consequently, an ideal thermal emitter is known as a
black body, and the radiation it emits is called
black-body radiation. (red) and
Wien approximation (blue). By the late 19th century, thermal radiation had been fairly well characterized experimentally. Several formulas that describe certain experimental measurements of thermal radiation had been developed.
Wien’s displacement law gives the relation between temperature and the wavelength at which the radiation is strongest, while the
Stefan–Boltzmann law describes the total power emitted per unit area. The best theoretical explanation of the experimental results was the
Rayleigh–Jeans law, which, as shown in the figure, agrees with experimental results well at large wavelengths (or, equivalently, low frequencies), but strongly disagrees at short wavelengths (or high frequencies). In fact, at short wavelengths, classical physics predicted that energy will be emitted by a hot body at an infinite rate. This result, which is clearly wrong, is known as the
ultraviolet catastrophe. Physicists searched for a single theory that explained all the experimental results. The first model that was able to explain the full spectrum of thermal radiation was put forward by
Max Planck in 1900. He proposed a mathematical model in which the thermal radiation was in equilibrium with a set of
harmonic oscillators. To reproduce the experimental results, he had to assume that each oscillator emitted an integer number of units of energy at its single characteristic frequency, rather than being able to emit any arbitrary amount of energy. In other words, the energy emitted by an oscillator was
quantized. According to Planck, the quantum of energy of a light quantum is proportional to its
frequency . As an equation is it written: E = h \nu. This is now known as the
Planck relation and the proportionality constant, , as the
Planck constant. Planck's law was the first quantum theory in physics, and Planck won the 1918
Nobel Prize in Physics "in recognition of the services he rendered to the advancement of Physics by his discovery of energy quanta". At the time, however, Planck's view was that quantization was purely a
heuristic mathematical construct, rather than (as is now believed) a fundamental change in our understanding of the world.
Einstein applies quanta to explain the photoelectric effect In 1887,
Heinrich Hertz observed that when light with sufficient frequency hits a metallic surface, the surface emits
cathode rays. This observation is at odds with classical electromagnetism, which predicts that the electron's energy should be proportional to the intensity of the incident radiation. 1905 In 1905,
Albert Einstein suggested that even though continuous models of light worked extremely well for time-averaged optical phenomena, for instantaneous transitions the energy in light may occur a finite number of energy quanta. In the introduction section of his March 1905 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 has been called the most "revolutionary" sentence written by a twentieth century physicist, meaning that it proposed an idea which altered mainstream thinking.
The energy of a single quantum of light of frequency f is given by the frequency multiplied by the Planck constant h: : E = hf Einstein assumed a light quanta transfers all of its energy to a single electron imparting at most an energy to the electron. Therefore, only the light frequency determines the maximum energy that can be imparted to the electron; the intensity of the photoemission is proportional to the light beam intensity. This amount of energy is different for each metal. If the energy of the light quanta is less than the work function, then it does not carry sufficient energy to remove the electron from the metal. The threshold frequency, , is the frequency of a light quanta whose energy is equal to the work function: : \varphi = h f_0. If is greater than , the energy is enough to remove an electron. The ejected electron has a
kinetic energy, , which is, at most, equal to the light energy minus the energy needed to dislodge the electron from the metal: : E_\text{k} = hf - \varphi = h(f - f_0). Einstein's description of light as being composed of energy quanta extended Planck's notion of quantized energy, which is that a single quantum of a given frequency, , delivers an invariant amount of energy, . Einstein was awarded the 1921 Nobel Prize in Physics "for his services to Theoretical Physics, and especially for his discovery of the law of the photoelectric effect". In nature, single quanta are rarely encountered. The Sun and emission sources available in the 19th century emit a vast amount of energy every second. The
Planck constant, , is so tiny that the amount of energy in each quantum, is very very small. Light we see includes many trillions of such quanta.
Arthur Compton's demonstration of the
scattering of light by electrons scattering convinced physicists of the reality of photons. Compton won the 1927 Nobel Prize in Physics for his discovery. The term "
photon" was introduced in 1926 by
Gilbert N. Lewis.
Quantization of matter: the Bohr model of the atom Ernest Rutherford's discovery of the atomic nucleus in 1911 did not immediately cause atomic models to be revised. Mechanical models with circulating electrons had been proposed for many years but they were known to be unstable. : \frac{1}{\lambda} = R \left(\frac{1}{m^2} - \frac{1}{n^2}\right), where
R is the
Rydberg constant, equal to 0.0110 nm−1, and
n must be greater than
m. The Rydberg formula accounts for the four visible wavelengths of hydrogen by setting and . It also predicts additional wavelengths in the emission spectrum: for and for , the emission spectrum should contain certain ultraviolet wavelengths, and for and , it should also contain certain infrared wavelengths. Experimental observation of these wavelengths came two decades later: in 1908
Louis Paschen found some of the predicted infrared wavelengths, and in 1914
Theodore Lyman found some of the predicted ultraviolet wavelengths. In "On the Constitution of Atoms and Molecules", he proposed
a new model of the atom that included quantized electron orbits. In the Bohr model, the hydrogen atom is pictured as a heavy, positively charged nucleus orbited by a light, negatively charged electron. The electron can only exist in certain, discretely separated orbits, labeled by their
angular momentum, which is restricted to be an integer multiple of the
reduced Planck constant. The electron moves to a higher or lower orbital by absorbing or emitting a photon of corresponding frequency. These orbits had fixed or quantized values of angular momentum, a concept proposed by
John William Nicholson in a nuclear atom model and adopted by Bohr in his model. When an atom emitted (or absorbed) energy, the electron did not move in a continuous trajectory from one orbit around the nucleus to another, as might be expected classically. Instead, the electron would jump instantaneously from one orbit to another, giving off the emitted light in the form of a photon. The possible energies of photons given off by each element were determined by the differences in energy between the orbits, and so the emission spectrum for each element would contain a number of lines. The model's key success lay in explaining the Rydberg formula for the spectral
emission lines of atomic hydrogen by using the transitions of electrons between orbits. While the Rydberg formula had been known experimentally, it did not gain a theoretical underpinning until the Bohr model was introduced. Not only did the Bohr model explain the reasons for the structure of the Rydberg formula, it also provided a justification for the fundamental physical constants that make up the formula's empirical results. Starting from only one simple assumption about the rule that the orbits must obey, the Bohr model was able to relate the observed spectral lines in the emission spectrum of hydrogen to previously known constants. In Bohr's model, the electron was not allowed to emit energy continuously and crash into the nucleus: once it was in the closest permitted orbit, it was stable forever. Bohr's model did not explain why the orbits should be quantized in that way, nor was it able to make accurate predictions for atoms with more than one electron, or to explain why some spectral lines are brighter than others. Some fundamental assumptions of the Bohr model were soon proven wrong—but the key result that the discrete lines in emission spectra are due to some property of the electrons in atoms being quantized is correct. The way that the electrons actually behave is strikingly different from Bohr's atom, and from what we see in the world of our everyday experience; this modern quantum mechanical model of the atom is discussed
below. Bohr theorized that the
angular momentum, , of an electron is quantized: : L = n\frac{h}{2\pi}=n\hbar where is an integer and and are the
Planck constant and Planck reduced constant respectively. Starting from this assumption,
Coulomb's law and the equations of
circular motion show that an electron with units of angular momentum orbits a proton at a distance given by : r = \frac{n^2 h^2}{4 \pi^2 k_e m e^2}, where is the
Coulomb constant, is the mass of an electron, and is the
charge on an electron. For simplicity this is written as : r = n^2 a_0,\! where , called the
Bohr radius, is equal to 0.0529 nm. The Bohr radius is the radius of the smallest allowed orbit. The energy of the electron is the sum of its
kinetic and
potential energies. The electron has kinetic energy by virtue of its actual motion around the nucleus, and potential energy because of its electromagnetic interaction with the nucleus. In the Bohr model this energy can be calculated, and is given by : E = -\frac{k_{\mathrm{e}}e^2}{2a_0} \frac{1}{n^2}. Thus Bohr's assumption that angular momentum is quantized means that an electron can inhabit only certain orbits around the nucleus and that it can have only certain energies. A consequence of these constraints is that the electron does not crash into the nucleus: it cannot continuously emit energy, and it cannot come closer to the nucleus than
a0 (the Bohr radius). An electron loses energy by jumping instantaneously from its original orbit to a lower orbit; the extra energy is emitted in the form of a photon. Conversely, an electron that absorbs a photon gains energy, hence it jumps to an orbit that is farther from the nucleus. Each photon from glowing atomic hydrogen is due to an electron moving from a higher orbit, with radius , to a lower orbit, . The energy of this photon is the difference in the energies and of the electron: : E_{\gamma} = E_n - E_m = \frac{k_{\mathrm{e}}e^2}{2a_0}\left(\frac{1}{m^2}-\frac{1}{n^2}\right) Since Planck's equation shows that the photon's energy is related to its wavelength by , the wavelengths of light that can be emitted are given by : \frac{1}{\lambda} = \frac{k_{\mathrm{e}}e^2}{2 a_0 h c}\left(\frac{1}{m^2}-\frac{1}{n^2}\right). This equation has the same form as the Rydberg formula, and predicts that the constant should be given by : R = \frac{k_{\mathrm{e}}e^2}{2 a_0 h c} . Therefore, the Bohr model of the atom can predict the emission spectrum of hydrogen in terms of fundamental constants. The model can be easily modified to account for the emission spectrum of any system consisting of a nucleus and a single electron (that is,
ions such as He+ or O7+, which contain only one electron) but cannot be extended to an atom with two electrons such as neutral helium. However, it was not able to make accurate predictions for multi-electron atoms, or to explain why some spectral lines are brighter than others. 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. 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 . They are collectively known as the
old quantum theory. Bohr was awarded the 1922 Nobel Prize in Physics "for his services in the investigation of the structure of atoms and of the radiation emanating from them".
Spin quantization Quantization of the orbital angular momentum of the electron combined with the magnetic moment of the electron suggested that atoms with a magnetic moment should show quantized behavior in a magnetic field. In 1922,
Otto Stern and
Walther Gerlach set out to test this theory. They heated silver in a vacuum tube equipped with a series of narrow aligned slits, creating a molecular beam of silver atoms. They shot this beam through an
inhomogeneous magnetic field. Rather than a continuous pattern of silver atoms, they found two bunches. Relative to its northern pole, pointing up, down, or somewhere in between, in classical mechanics, a magnet thrown through a magnetic field may be deflected a small or large distance upwards or downwards. The atoms that Stern and Gerlach shot through the magnetic field acted similarly. However, while the magnets could be deflected variable distances, the atoms would always be deflected a constant distance either up or down. This implied that the property of the atom that corresponds to the magnet's orientation must be quantized, taking one of two values (either up or down), as opposed to being chosen freely from any angle. The choice of the orientation of the magnetic field used in the Stern–Gerlach experiment is arbitrary. In the animation shown here, the field is vertical and so the atoms are deflected either up or down. If the magnet is rotated a quarter turn, the atoms are deflected either left or right. Using a vertical field shows that the spin along the vertical axis is quantized, and using a horizontal field shows that the spin along the horizontal axis is quantized. The results of the Stern-Gerlach experiment caused a sensation, most especially because leading scientists, including Einstein and
Paul Ehrenfest argued that the silver atoms should have random orientations in the conditions of the experiment: quantization should not have been observable. In 1925,
Ralph Kronig proposed that electrons behave as if they self-rotate, or "spin", about an axis. Spin would generate a tiny magnetic moment that would split the energy levels responsible for spectral lines, in agreement with existing measurements. Two electrons in the same orbital would occupy distinct
quantum states if they "spun" in opposite directions thus satisfying the exclusion principle. Unfortunately, the theory had two significant flaws: two values computed by Kronig were off by a factor of two. Kronig's senior colleagues discouraged his work and it was never published. Ten months later, Dutch physicists
George Uhlenbeck and
Samuel Goudsmit at
Leiden University published their theory of electron self rotation. The model, like Kronig's was essentially classical but resulted in a quantum prediction.
de Broglie's matter wave hypothesis in 1929. De Broglie won the
Nobel Prize in Physics for his prediction that matter acts as a wave, made in his 1924 PhD thesis. In 1924,
Louis de Broglie published a breakthrough hypothesis:
matter has wave properties. Building on Einstein's proposal that the photoelectric effect can be described using quantized energy transfers and by Einstein's separate proposal, from special relativity, that mass at rest is equivalent to energy via E=m_0c^2, de Broglie proposed that matter in motion appears to have an associated wave with wavelength \lambda=h/p where p is the matter momentum from the motion. Requiring his wavelength to encircle an atom, he explained quantization of Bohr's orbits. De Broglie's treatment of the Bohr atom was ultimately unsuccessful, but his hypothesis served as a starting point for Schrödinger's wave equation. Matter behaving as a wave was first demonstrated experimentally: a beam of electrons can exhibit
diffraction, just like a beam of light or a water wave. Three years after de Broglie published his hypothesis two different groups demonstrated electron diffraction. At the
University of Aberdeen,
George Paget Thomson and Alexander Reid passed a beam of electrons through a thin celluloid film, then later metal films, and observed the predicted interference patterns. (Alexander Reid, who was Thomson's graduate student, performed the first experiments but he died soon after in a motorcycle accident and is rarely mentioned.) At
Bell Labs,
Clinton Joseph Davisson and
Lester Halbert Germer reflected an electron beam from a nickel sample in their experiment, observing well-defined beams predicted by wave models returning from the crystal. Thomson and Davisson shared the Nobel Prize for Physics in 1937 for their experimental work. == Development of modern quantum mechanics ==