Quantum mechanics is the science of the very small. It explains the behavior of matter and its interactions with energy on the scale of atoms and subatomic particles. By contrast, classical physics explains matter and energy only on a scale familiar to human experience, including the behavior of astronomical bodies such as the Moon. Classical physics is still used in much of modern science and technology. However, towards the end of the 19th century, scientists discovered phenomena in both the large (macro) and the small (micro) worlds that classical physics could not explain. The desire to resolve inconsistencies between observed phenomena and classical theory led to two major revolutions in physics that created a shift in the original scientific paradigm: the theory of relativity and the development of quantum mechanics. This article describes how physicists discovered the limitations of classical physics and developed the main concepts of the quantum theory that replaced it in the early decades of the 20th century. It describes these concepts in roughly the order in which they were first discovered. For a more complete history of the subject, see History of quantum mechanics.
Light behaves in some aspects like particles and in other aspects like waves. Matter—the "stuff" of the universe consisting of particles such as electrons and atoms—exhibits wavelike behavior too. Some light sources, such as neon lights, give off only certain frequencies of light. Quantum mechanics shows that light, along with all other forms of electromagnetic radiation, comes in discrete units, called photons, and predicts its energies, colors, and spectral intensities. A single photon is a quantum, or smallest observable amount, of the electromagnetic field because a partial photon has never been observed. More broadly, quantum mechanics shows that many quantities, such as angular momentum, that appeared continuous in the zoomed-out view of classical mechanics, turn out to be (at the small, zoomed-in scale of quantum mechanics) quantized. Angular momentum is required to take on one of a set of discrete allowable values, and since the gap between these values is so minute, the discontinuity is only apparent at the atomic level.
Many aspects of quantum mechanics are counterintuitive and can seem paradoxical, because they describe behavior quite different from that seen at larger scales. In the words of quantum physicist Richard Feynman, quantum mechanics deals with "nature as She is – absurd". For example, the uncertainty principle of quantum mechanics means that the more closely one pins down one measurement (such as the position of a particle), the less accurate another measurement pertaining to the same particle (such as its momentum) must become.
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 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.
In the late 19th century, thermal radiation had been fairly well characterized experimentally.[note 1] However, classical physics led to the Rayleigh–Jeans law, which, as shown in the figure, agrees with experimental results well at low frequencies, but strongly disagrees at high frequencies. 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.[note 2] The quantum of energy for each oscillator, according to Planck, was proportional to the frequency of the oscillator; the constant of proportionality is now known as the Planck constant. The Planck constant, usually written as h, has the value of 6.63×10−34 J s. So, the energy E of an oscillator of frequency f is given by
To change the color of such a radiating body, it is necessary to change its temperature. Planck's law explains why: increasing the temperature of a body allows it to emit more energy overall, and means that a larger proportion of the energy is towards the violet end of the spectrum.
Planck's law was the first quantum theory in physics, and Planck won the Nobel Prize in 1918 "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.
In 1905, Albert Einstein took an extra step. He suggested that quantization was not just a mathematical construct, but that the energy in a beam of light actually occurs in individual packets, which are now called photons. The energy of a single photon is given by its frequency multiplied by Planck's constant:
For centuries, scientists had debated between two possible theories of light: was it a wave or did it instead comprise a stream of tiny particles? By the 19th century, the debate was generally considered to have been settled in favor of the wave theory, as it was able to explain observed effects such as refraction, diffraction, interference, and polarization. James Clerk Maxwell had shown that electricity, magnetism and light are all manifestations of the same phenomenon: the electromagnetic field. Maxwell's equations, which are the complete set of laws of classical electromagnetism, describe light as waves: a combination of oscillating electric and magnetic fields. Because of the preponderance of evidence in favor of the wave theory, Einstein's ideas were met initially with great skepticism. Eventually, however, the photon model became favored. One of the most significant pieces of evidence in its favor was its ability to explain several puzzling properties of the photoelectric effect, described in the following section. Nonetheless, the wave analogy remained indispensable for helping to understand other characteristics of light: diffraction, refraction, and interference.
In 1887, Heinrich Hertz observed that when light with sufficient frequency hits a metallic surface, it emits electrons. In 1902, Philipp Lenard discovered that the maximum possible energy of an ejected electron is related to the frequency of the light, not to its intensity: if the frequency is too low, no electrons are ejected regardless of the intensity. Strong beams of light toward the red end of the spectrum might produce no electrical potential at all, while weak beams of light toward the violet end of the spectrum would produce higher and higher voltages. The lowest frequency of light that can cause electrons to be emitted, called the threshold frequency, is different for different metals. This observation is at odds with classical electromagnetism, which predicts that the electron's energy should be proportional to the intensity of the radiation.:24 So when physicists first discovered devices exhibiting the photoelectric effect, they initially expected that a higher intensity of light would produce a higher voltage from the photoelectric device.
Einstein explained the effect by postulating that a beam of light is a stream of particles ("photons") and that, if the beam is of frequency f, then each photon has an energy equal to hf. An electron is likely to be struck only by a single photon, which imparts at most an energy hf to the electron. Therefore, the intensity of the beam has no effect[note 3] and only its frequency determines the maximum energy that can be imparted to the electron.
To explain the threshold effect, Einstein argued that it takes a certain amount of energy, called the work function and denoted by φ, to remove an electron from the metal. This amount of energy is different for each metal. If the energy of the photon is less than the work function, then it does not carry sufficient energy to remove the electron from the metal. The threshold frequency, f0, is the frequency of a photon whose energy is equal to the work function:
If f is greater than f0, the energy hf is enough to remove an electron. The ejected electron has a kinetic energy, EK, which is, at most, equal to the photon's energy minus the energy needed to dislodge the electron from the metal:
Einstein's description of light as being composed of particles extended Planck's notion of quantized energy, which is that a single photon of a given frequency, f, delivers an invariant amount of energy, hf. In other words, individual photons can deliver more or less energy, but only depending on their frequencies. In nature, single photons are rarely encountered. The Sun and emission sources available in the 19th century emit vast numbers of photons every second, and so the importance of the energy carried by each individual photon was not obvious. Einstein's idea that the energy contained in individual units of light depends on their frequency made it possible to explain experimental results that had seemed counterintuitive. However, although the photon is a particle, it was still being described as having the wave-like property of frequency. Effectively, the account of light as a particle is insufficient, and its wave-like nature is still required.[note 4]
The relationship between the frequency of electromagnetic radiation and the energy of each individual photon is why ultraviolet light can cause sunburn, but visible or infrared light cannot. A photon of ultraviolet light delivers a high amount of energy—enough to contribute to cellular damage such as occurs in a sunburn. A photon of infrared light delivers less energy—only enough to warm one's skin. So, an infrared lamp can warm a large surface, perhaps large enough to keep people comfortable in a cold room, but it cannot give anyone a sunburn.
All photons of the same frequency have identical energy, and all photons of different frequencies have proportionally (order 1, Ephoton = hf ) different energies. However, although the energy imparted by photons is invariant at any given frequency, the initial energy state of the electrons in a photoelectric device prior to absorption of light is not necessarily uniform. Anomalous results may occur in the case of individual electrons. For instance, an electron that was already excited above the equilibrium level of the photoelectric device might be ejected when it absorbed uncharacteristically low frequency illumination. Statistically, however, the characteristic behavior of a photoelectric device reflects the behavior of the vast majority of its electrons, which are at their equilibrium level. This point is helpful in comprehending the distinction between the study of individual particles in quantum dynamics and the study of massed particles in classical physics.
By the dawn of the 20th century, evidence required a model of the atom with a diffuse cloud of negatively charged electrons surrounding a small, dense, positively charged nucleus. These properties suggested a model in which electrons circle around the nucleus like planets orbiting a sun.[note 5] However, it was also known that the atom in this model would be unstable: according to classical theory, orbiting electrons are undergoing centripetal acceleration, and should therefore give off electromagnetic radiation, the loss of energy also causing them to spiral toward the nucleus, colliding with it in a fraction of a second.
A second, related puzzle was the emission spectrum of atoms. When a gas is heated, it gives off light only at discrete frequencies. For example, the visible light given off by hydrogen consists of four different colors, as shown in the picture below. The intensity of the light at different frequencies is also different. By contrast, white light consists of a continuous emission across the whole range of visible frequencies. By the end of the nineteenth century, a simple rule known as Balmer's formula showed how the frequencies of the different lines related to each other, though without explaining why this was, or making any prediction about the intensities. The formula also predicted some additional spectral lines in ultraviolet and infrared light that had not been observed at the time. These lines were later observed experimentally, raising confidence in the value of the formula.
In 1913 Niels Bohr proposed a new model of the atom that included quantized electron orbits: electrons still orbit the nucleus much as planets orbit around the sun, but they are permitted to inhabit only certain orbits, not to orbit at any distance. 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.
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 didn't 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.
Matter behaving as a wave was first demonstrated experimentally for electrons: a beam of electrons can exhibit diffraction, just like a beam of light or a water wave.[note 8] Similar wave-like phenomena were later shown for atoms and even molecules.
The relationship, called the de Broglie hypothesis, holds for all types of matter: all matter exhibits properties of both particles and waves.
The concept of wave–particle duality says that neither the classical concept of "particle" nor of "wave" can fully describe the behavior of quantum-scale objects, either photons or matter. Wave–particle duality is an example of the principle of complementarity in quantum physics. An elegant example of wave–particle duality, the double slit experiment, is discussed in the section below.
In the double-slit experiment, as originally performed by Thomas Young and Augustin Fresnel in 1827, a beam of light is directed through two narrow, closely spaced slits, producing an interference pattern of light and dark bands on a screen. If one of the slits is covered up, one might naively expect that the intensity of the fringes due to interference would be halved everywhere. In fact, a much simpler pattern is seen, a simple diffraction pattern. Closing one slit results in a much simpler pattern diametrically opposite the open slit. Exactly the same behavior can be demonstrated in water waves, and so the double-slit experiment was seen as a demonstration of the wave nature of light.
Variations of the double-slit experiment have been performed using electrons, atoms, and even large molecules, and the same type of interference pattern is seen. Thus it has been demonstrated that all matter possesses both particle and wave characteristics.
Even if the source intensity is turned down, so that only one particle (e.g. photon or electron) is passing through the apparatus at a time, the same interference pattern develops over time. The quantum particle acts as a wave when passing through the double slits, but as a particle when it is detected. This is a typical feature of quantum complementarity: a quantum particle acts as a wave in an experiment to measure its wave-like properties, and like a particle in an experiment to measure its particle-like properties. The point on the detector screen where any individual particle shows up is the result of a random process. However, the distribution pattern of many individual particles mimics the diffraction pattern produced by waves.
De Broglie expanded the Bohr model of the atom by showing that an electron in orbit around a nucleus could be thought of as having wave-like properties. In particular, an electron is observed only in situations that permit a standing wave around a nucleus. An example of a standing wave is a violin string, which is fixed at both ends and can be made to vibrate. The waves created by a stringed instrument appear to oscillate in place, moving from crest to trough in an up-and-down motion. The wavelength of a standing wave is related to the length of the vibrating object and the boundary conditions. For example, because the violin string is fixed at both ends, it can carry standing waves of wavelengths , where l is the length and n is a positive integer. De Broglie suggested that the allowed electron orbits were those for which the circumference of the orbit would be an integer number of wavelengths. The electron's wavelength therefore determines that only Bohr orbits of certain distances from the nucleus are possible. In turn, at any distance from the nucleus smaller than a certain value it would be impossible to establish an orbit. The minimum possible distance from the nucleus is called the Bohr radius.
De Broglie's treatment of quantum events served as a starting point for Schrödinger when he set out to construct a wave equation to describe quantum theoretical events.
In 1922, Otto Stern and Walther Gerlach shot silver atoms through an inhomogeneous magnetic field. In classical mechanics, a magnet thrown through a magnetic field may be, depending on its orientation (if it is pointing with its northern pole upwards or down, or somewhere in between), deflected a small or large distance upwards or downwards. The atoms that Stern and Gerlach shot through the magnetic field acted in a similar way. 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.
Ralph Kronig originated the theory that particles such as atoms or electrons behave as if they rotate, or "spin", about an axis. Spin would account for the missing magnetic moment, and allow two electrons in the same orbital to occupy distinct quantum states if they "spun" in opposite directions, thus satisfying the exclusion principle. The quantum number represented the sense (positive or negative) of spin.
The choice of 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.
If, instead of hitting a detector screen, one of the beams of atoms coming out of the Stern–Gerlach apparatus is passed into another (inhomogeneous) magnetic field oriented in the same direction, all of the atoms are deflected the same way in this second field. However, if the second field is oriented at 90° to the first, then half of the atoms are deflected one way and half the other, so that the atom's spin about the horizontal and vertical axes are independent of each other. However, if one of these beams (e.g. the atoms that were deflected up then left) is passed into a third magnetic field, oriented the same way as the first, half of the atoms go one way and half the other, even though they all went in the same direction originally. The action of measuring the atoms' spin with respect to a horizontal field has changed their spin with respect to a vertical field.
The Stern–Gerlach experiment demonstrates a number of important features of quantum mechanics:
In 1925, Werner Heisenberg attempted to solve one of the problems that the Bohr model left unanswered, explaining the intensities of the different lines in the hydrogen emission spectrum. Through a series of mathematical analogies, he wrote out the quantum-mechanical analog for the classical computation of intensities. Shortly afterwards, Heisenberg's colleague Max Born realised that Heisenberg's method of calculating the probabilities for transitions between the different energy levels could best be expressed by using the mathematical concept of matrices.[note 9]
In the same year, building on de Broglie's hypothesis, Erwin Schrödinger developed the equation that describes the behavior of a quantum-mechanical wave. The mathematical model, called the Schrödinger equation after its creator, is central to quantum mechanics, defines the permitted stationary states of a quantum system, and describes how the quantum state of a physical system changes in time. The wave itself is described by a mathematical function known as a "wave function". Schrödinger said that the wave function provides the "means for predicting probability of measurement results".
Schrödinger was able to calculate the energy levels of hydrogen by treating a hydrogen atom's electron as a classical wave, moving in a well of electrical potential created by the proton. This calculation accurately reproduced the energy levels of the Bohr model.
In May 1926, Schrödinger proved that Heisenberg's matrix mechanics and his own wave mechanics made the same predictions about the properties and behavior of the electron; mathematically, the two theories had an underlying common form. Yet the two men disagreed on the interpretation of their mutual theory. For instance, Heisenberg accepted the theoretical prediction of jumps of electrons between orbitals in an atom, but Schrödinger hoped that a theory based on continuous wave-like properties could avoid what he called (as paraphrased by Wilhelm Wien) "this nonsense about quantum jumps".
Bohr, Heisenberg, and others tried to explain what these experimental results and mathematical models really mean. Their description, known as the Copenhagen interpretation of quantum mechanics, aimed to describe the nature of reality that was being probed by the measurements and described by the mathematical formulations of quantum mechanics.
The main principles of the Copenhagen interpretation are:
Various consequences of these principles are discussed in more detail in the following subsections.
Suppose it is desired to measure the position and speed of an object – for example a car going through a radar speed trap. It can be assumed that the car has a definite position and speed at a particular moment in time. How accurately these values can be measured depends on the quality of the measuring equipment. If the precision of the measuring equipment is improved, it provides a result closer to the true value. It might be assumed that the speed of the car and its position could be operationally defined and measured simultaneously, as precisely as might be desired.
In 1927, Heisenberg proved that this last assumption is not correct. Quantum mechanics shows that certain pairs of physical properties, for example position and speed, cannot be simultaneously measured, nor defined in operational terms, to arbitrary precision: the more precisely one property is measured, or defined in operational terms, the less precisely can the other. This statement is known as the uncertainty principle. The uncertainty principle is not only a statement about the accuracy of our measuring equipment, but, more deeply, is about the conceptual nature of the measured quantities – the assumption that the car had simultaneously defined position and speed does not work in quantum mechanics. On a scale of cars and people, these uncertainties are negligible, but when dealing with atoms and electrons they become critical.
Heisenberg gave, as an illustration, the measurement of the position and momentum of an electron using a photon of light. In measuring the electron's position, the higher the frequency of the photon, the more accurate is the measurement of the position of the impact of the photon with the electron, but the greater is the disturbance of the electron. This is because from the impact with the photon, the electron absorbs a random amount of energy, rendering the measurement obtained of its momentum increasingly uncertain (momentum is velocity multiplied by mass), for one is necessarily measuring its post-impact disturbed momentum from the collision products and not its original momentum. With a photon of lower frequency, the disturbance (and hence uncertainty) in the momentum is less, but so is the accuracy of the measurement of the position of the impact.
The uncertainty principle shows mathematically that the product of the uncertainty in the position and momentum of a particle (momentum is velocity multiplied by mass) could never be less than a certain value, and that this value is related to Planck's constant.
Wave function collapse is a forced expression for whatever just happened when it becomes appropriate to replace the description of an uncertain state of a system by a description of the system in a definite state. Explanations for the nature of the process of becoming certain are controversial. At any time before a photon "shows up" on a detection screen it can be described only with a set of probabilities for where it might show up. When it does show up, for instance in the CCD of an electronic camera, the time and the space where it interacted with the device are known within very tight limits. However, the photon has disappeared, and the wave function has disappeared with it. In its place some physical change in the detection screen has appeared, e.g., an exposed spot in a sheet of photographic film, or a change in electric potential in some cell of a CCD.
Because of the uncertainty principle, statements about both the position and momentum of particles can assign only a probability that the position or momentum has some numerical value. Therefore, it is necessary to formulate clearly the difference between the state of something that is indeterminate, such as an electron in a probability cloud, and the state of something having a definite value. When an object can definitely be "pinned-down" in some respect, it is said to possess an eigenstate.
In the Stern–Gerlach experiment discussed above, the spin of the atom about the vertical axis has two eigenstates: up and down. Before measuring it, we can only say that any individual atom has equal probability of being found to have spin up or spin down. The measurement process causes the wavefunction to collapse into one of the two states.
The eigenstates of spin about the vertical axis are not simultaneously eigenstates of spin about the horizontal axis, so this atom has equal probability of being found to have either value of spin about the horizontal axis. As described in the section above, measuring the spin about the horizontal axis can allow an atom that was spun up to spin down: measuring its spin about the horizontal axis collapses its wave function into one of the eigenstates of this measurement, which means it is no longer in an eigenstate of spin about the vertical axis, so can take either value.
In 1924, Wolfgang Pauli proposed a new quantum degree of freedom (or quantum number), with two possible values, to resolve inconsistencies between observed molecular spectra and the predictions of quantum mechanics. In particular, the spectrum of atomic hydrogen had a doublet, or pair of lines differing by a small amount, where only one line was expected. Pauli formulated his exclusion principle, stating, "There cannot exist an atom in such a quantum state that two electrons within [it] have the same set of quantum numbers."
Bohr's model of the atom was essentially a planetary one, with the electrons orbiting around the nuclear "sun". However, the uncertainty principle states that an electron cannot simultaneously have an exact location and velocity in the way that a planet does. Instead of classical orbits, electrons are said to inhabit atomic orbitals. An orbital is the "cloud" of possible locations in which an electron might be found, a distribution of probabilities rather than a precise location. Each orbital is three dimensional, rather than the two dimensional orbit, and is often depicted as a three-dimensional region within which there is a 95 percent probability of finding the electron.
Schrödinger was able to calculate the energy levels of hydrogen by treating a hydrogen atom's electron as a wave, represented by the "wave function" Ψ, in an electric potential well, V, created by the proton. The solutions to Schrödinger's equation are distributions of probabilities for electron positions and locations. Orbitals have a range of different shapes in three dimensions. The energies of the different orbitals can be calculated, and they accurately match the energy levels of the Bohr model.
Within Schrödinger's picture, each electron has four properties:
The collective name for these properties is the quantum state of the electron. The quantum state can be described by giving a number to each of these properties; these are known as the electron's quantum numbers. The quantum state of the electron is described by its wave function. The Pauli exclusion principle demands that no two electrons within an atom may have the same values of all four numbers.
The first property describing the orbital is the principal quantum number, n, which is the same as in Bohr's model. n denotes the energy level of each orbital. The possible values for n are integers:
The next quantum number, the azimuthal quantum number, denoted l, describes the shape of the orbital. The shape is a consequence of the angular momentum of the orbital. The angular momentum represents the resistance of a spinning object to speeding up or slowing down under the influence of external force. The azimuthal quantum number represents the orbital angular momentum of an electron around its nucleus. The possible values for l are integers from 0 to n − 1 (where n is the principal quantum number of the electron):
The shape of each orbital is usually referred to by a letter, rather than by its azimuthal quantum number. The first shape (l=0) is denoted by the letter s (a mnemonic being "sphere"). The next shape is denoted by the letter p and has the form of a dumbbell. The other orbitals have more complicated shapes (see atomic orbital), and are denoted by the letters d, f, g, etc.
The third quantum number, the magnetic quantum number, describes the magnetic moment of the electron, and is denoted by ml (or simply m). The possible values for ml are integers from −l to l (where l is the azimuthal quantum number of the electron):
The magnetic quantum number measures the component of the angular momentum in a particular direction. The choice of direction is arbitrary; conventionally the z-direction is chosen.
The fourth quantum number, the spin quantum number (pertaining to the "orientation" of the electron's spin) is denoted ms, with values +1⁄2 or −1⁄2.
The chemist Linus Pauling wrote, by way of example:
In the case of a helium atom with two electrons in the 1s orbital, the Pauli Exclusion Principle requires that the two electrons differ in the value of one quantum number. Their values of n, l, and ml are the same. Accordingly they must differ in the value of ms, which can have the value of +1⁄2 for one electron and −1⁄2 for the other."
It is the underlying structure and symmetry of atomic orbitals, and the way that electrons fill them, that leads to the organisation of the periodic table. The way the atomic orbitals on different atoms combine to form molecular orbitals determines the structure and strength of chemical bonds between atoms.
In 1928, Paul Dirac extended the Pauli equation, which described spinning electrons, to account for special relativity. The result was a theory that dealt properly with events, such as the speed at which an electron orbits the nucleus, occurring at a substantial fraction of the speed of light. By using the simplest electromagnetic interaction, Dirac was able to predict the value of the magnetic moment associated with the electron's spin, and found the experimentally observed value, which was too large to be that of a spinning charged sphere governed by classical physics. He was able to solve for the spectral lines of the hydrogen atom, and to reproduce from physical first principles Sommerfeld's successful formula for the fine structure of the hydrogen spectrum.
Dirac's equations sometimes yielded a negative value for energy, for which he proposed a novel solution: he posited the existence of an antielectron and of a dynamical vacuum. This led to the many-particle quantum field theory.
The Pauli exclusion principle says that two electrons in one system cannot be in the same state. Nature leaves open the possibility, however, that two electrons can have both states "superimposed" over each of them. Recall that the wave functions that emerge simultaneously from the double slits arrive at the detection screen in a state of superposition. Nothing is certain until the superimposed waveforms "collapse". At that instant an electron shows up somewhere in accordance with the probability that is the square of the absolute value of the sum of the complex-valued amplitudes of the two superimposed waveforms. The situation there is already very abstract. A concrete way of thinking about entangled photons, photons in which two contrary states are superimposed on each of them in the same event, is as follows:
Imagine that the superposition of a state labeled blue, and another state labeled red then appear (in imagination) as a purple state. Two photons are produced as the result of the same atomic event. Perhaps they are produced by the excitation of a crystal that characteristically absorbs a photon of a certain frequency and emits two photons of half the original frequency. So the two photons come out purple. If the experimenter now performs some experiment that determines whether one of the photons is either blue or red, then that experiment changes the photon involved from one having a superposition of blue and red characteristics to a photon that has only one of those characteristics. The problem that Einstein had with such an imagined situation was that if one of these photons had been kept bouncing between mirrors in a laboratory on earth, and the other one had traveled halfway to the nearest star, when its twin was made to reveal itself as either blue or red, that meant that the distant photon now had to lose its purple status too. So whenever it might be investigated after its twin had been measured, it would necessarily show up in the opposite state to whatever its twin had revealed.
In trying to show that quantum mechanics was not a complete theory, Einstein started with the theory's prediction that two or more particles that have interacted in the past can appear strongly correlated when their various properties are later measured. He sought to explain this seeming interaction in a classical way, through their common past, and preferably not by some "spooky action at a distance". The argument is worked out in a famous paper, Einstein, Podolsky, and Rosen (1935; abbreviated EPR), setting out what is now called the EPR paradox. Assuming what is now usually called local realism, EPR attempted to show from quantum theory that a particle has both position and momentum simultaneously, while according to the Copenhagen interpretation, only one of those two properties actually exists and only at the moment that it is being measured. EPR concluded that quantum theory is incomplete in that it refuses to consider physical properties that objectively exist in nature. (Einstein, Podolsky, & Rosen 1935 is currently Einstein's most cited publication in physics journals.) In the same year, Erwin Schrödinger used the word "entanglement" and declared: "I would not call that one but rather the characteristic trait of quantum mechanics." The question of whether entanglement is a real condition is still in dispute. The Bell inequalities are the most powerful challenge to Einstein's claims.
The idea of quantum field theory began in the late 1920s with British physicist Paul Dirac, when he attempted to quantize the electromagnetic field – a procedure for constructing a quantum theory starting from a classical theory.
Merriam-Webster defines a field in physics as "a region or space in which a given effect (such as magnetism) exists". Other effects that manifest themselves as fields are gravitation and static electricity. In 2008, physicist Richard Hammond wrote:
Sometimes we distinguish between quantum mechanics (QM) and quantum field theory (QFT). QM refers to a system in which the number of particles is fixed, and the fields (such as the electromechanical field) are continuous classical entities. QFT ... goes a step further and allows for the creation and annihilation of particles ...
He added, however, that quantum mechanics is often used to refer to "the entire notion of quantum view".:108
In 1931, Dirac proposed the existence of particles that later became known as antimatter. Dirac shared the Nobel Prize in Physics for 1933 with Schrödinger "for the discovery of new productive forms of atomic theory".
On its face, quantum field theory allows infinite numbers of particles, and leaves it up to the theory itself to predict how many and with which probabilities or numbers they should exist. When developed further, the theory often contradicts observation, so that its creation and annihilation operators can be empirically tied down. Furthermore, empirical conservation laws such as that of mass–energy suggest certain constraints on the mathematical form of the theory, which are mathematically speaking finicky. The latter fact makes quantum field theories difficult to handle, but has also led to further restrictions on admissible forms of the theory; the complications are mentioned below under the rubric of renormalization.
Quantum electrodynamics (QED) is the name of the quantum theory of the electromagnetic force. Understanding QED begins with understanding electromagnetism. Electromagnetism can be called "electrodynamics" because it is a dynamic interaction between electrical and magnetic forces. Electromagnetism begins with the electric charge.
Electric charges are the sources of, and create, electric fields. An electric field is a field that exerts a force on any particles that carry electric charges, at any point in space. This includes the electron, proton, and even quarks, among others. As a force is exerted, electric charges move, a current flows, and a magnetic field is produced. The changing magnetic field, in turn, causes electric current (often moving electrons). The physical description of interacting charged particles, electrical currents, electrical fields, and magnetic fields is called electromagnetism.
In 1928 Paul Dirac produced a relativistic quantum theory of electromagnetism. This was the progenitor to modern quantum electrodynamics, in that it had essential ingredients of the modern theory. However, the problem of unsolvable infinities developed in this relativistic quantum theory. Years later, renormalization largely solved this problem. Initially viewed as a suspect, provisional procedure by some of its originators, renormalization eventually was embraced as an important and self-consistent tool in QED and other fields of physics. Also, in the late 1940s Feynman's diagrams depicted all possible interactions pertaining to a given event. The diagrams showed in particular that the electromagnetic force is the exchange of photons between interacting particles.
The Lamb shift is an example of a quantum electrodynamics prediction that has been experimentally verified. It is an effect whereby the quantum nature of the electromagnetic field makes the energy levels in an atom or ion deviate slightly from what they would otherwise be. As a result, spectral lines may shift or split.
Similarly, within a freely propagating electromagnetic wave, the current can also be just an abstract displacement current, instead of involving charge carriers. In QED, its full description makes essential use of short lived virtual particles. There, QED again validates an earlier, rather mysterious concept.
In the 1960s physicists realized that QED broke down at extremely high energies. From this inconsistency the Standard Model of particle physics was discovered, which remedied the higher energy breakdown in theory. It is another extended quantum field theory that unifies the electromagnetic and weak interactions into one theory. This is called the electroweak theory.
Additionally the Standard Model contains a high energy unification of the electroweak theory with the strong force, described by quantum chromodynamics. It also postulates a connection with gravity as yet another gauge theory, but the connection is as of 2015 still poorly understood. The theory's successful prediction of the Higgs particle to explain inertial mass was confirmed by the Large Hadron Collider, and thus the Standard model is now considered the basic and more or less complete description of particle physics as we know it.
The physical measurements, equations, and predictions pertinent to quantum mechanics are all consistent and hold a very high level of confirmation. However, the question of what these abstract models say about the underlying nature of the real world has received competing answers. These interpretations are widely varying and sometimes somewhat abstract. For instance, the Copenhagen interpretation states that before a measurement, statements about a particles' properties are completely meaningless, while in the Many-worlds interpretation describes the existence of a multiverse made up of every possible universe.
Applications of quantum mechanics include the laser, the transistor, the electron microscope, and magnetic resonance imaging. A special class of quantum mechanical applications is related to macroscopic quantum phenomena such as superfluid helium and superconductors. The study of semiconductors led to the invention of the diode and the transistor, which are indispensable for modern electronics.
In even the simple light switch, quantum tunnelling is absolutely vital, as otherwise the electrons in the electric current could not penetrate the potential barrier made up of a layer of oxide. Flash memory chips found in USB drives also use quantum tunnelling, to erase their memory cells.
[I]n a three-grating interferometer... We observe high-contrast quantum fringe patterns of molecules... having 810 atoms in a single particle.
Received July 29, 1925See Werner Heisenberg's paper, "Quantum-Theoretical Re-interpretation of Kinematic and Mechanical Relations" pp. 261–276
His great discovery, Schrödinger's wave equation, was made at the end of this epoch-during the first half of 1926.
The following titles, all by working physicists, attempt to communicate quantum theory to lay people, using a minimum of technical apparatus.
The Bohr radius (a0 or rBohr) is a physical constant, approximately equal to the most probable distance between the nucleus and the electron in a hydrogen atom in its ground state. It is named after Niels Bohr, due to its role in the Bohr model of an atom. Its value is 5.2917721067(12)×10−11 m.David J. Griffiths
David Jeffrey Griffiths (born 1942) is a U.S. physicist and educator. He worked at Reed College from 1978 through 2009, becoming the Howard Vollum Professor of Science before his retirement. He is not to be confused with the late physicist David J. Griffiths (David John Griffiths) of Oregon State University.Edgar Bright Wilson
Edgar Bright Wilson Jr. (December 18, 1908 – June 12, 1992) was an American chemist.Wilson was a prominent and accomplished chemist and teacher, recipient of the National Medal of Science in 1975, Guggenheim Fellowships in 1949 and 1970, the Elliott Cresson Medal in 1982, and a number of honorary doctorates. He was also the Theodore William Richards Professor of Chemistry, Emeritus at Harvard University. One of his sons, Kenneth G. Wilson, was awarded the Nobel Prize in physics in 1982.
E. B. Wilson was a student and protégé of Nobel Laureate Linus Pauling and was a coauthor with Pauling of Introduction to Quantum Mechanics, a graduate level textbook in Quantum Mechanics. Wilson was also the thesis advisor of Nobel Laureate Dudley Herschbach. Wilson was elected to the first class of the Harvard Society of Fellows.
Wilson made major contributions to the field of molecular spectroscopy. He developed the first rigorous quantum mechanical Hamiltonian in internal coordinates for a polyatomic molecule. He developed the theory of how rotational spectra are influenced by centrifugal distortion during rotation. He pioneered the use of group theory for the analysis and simplification normal mode analysis, particularly for high symmetry molecules, such as benzene. In 1955, with J.C. Decius and Paul C. Cross, Wilson published Molecular Vibrations, still the primary reference text for the theoretical analysis of vibrational spectroscopy, including the GF matrix method that Wilson had developed. Following the Second World War, Wilson was a pioneer in the application of microwave spectroscopy to the determination of molecular structure. Wilson wrote an influential introductory text Introduction to Scientific Research that provided an introduction of all the steps of scientific research, from defining a problem through the archival of data after publication.
Starting in 1997, the American Chemical Society has annually awarded the E. Bright Wilson Award in Spectroscopy, named in honor of Wilson.George C. Schatz
George C. Schatz (born April 14, 1949), the Morrison Professor of Chemistry at Northwestern University, is a theoretical chemist best known for his seminal contributions to the field of reaction dynamics. Born in Watertown, New York, he obtained his B. S. from Clarkson University in 1971 and his Ph.D. from Caltech in 1976 under Aron Kuppermann. Following postdoctoral work at MIT, he joined the Chemistry Department at Northwestern University.
A longtime senior editor of the Journal of Physical Chemistry, he became its editor-in-chief in 2005. The journal previously (1997) having been split in Journal of Physical Chemistry A (molecular physical chemistry, both theoretical and experimental) and Journal of Physical Chemistry B (solid state, soft matter, liquids), Schatz initiated the spin-off of a third journal, Journal of Physical Chemistry C, focusing on nanotechnology and molecular electronics.
Schatz is a member of the National Academy of Sciences, of the International Academy of Quantum Molecular Science, and many other such bodies. He authored over 350 scientific papers, and co-authored two books with his colleague Mark A. Ratner: Introduction to Quantum Mechanics in Chemistry and Quantum Mechanics in Chemistry
Recently much of Schatz's research has been concerned with nanotechnology and bionanotechnology.Glossary of elementary quantum mechanics
This is a glossary for the terminology often encountered in undergraduate quantum mechanics courses.
Cautions:Heisenberg's entryway to matrix mechanics
For more context, see Introduction to quantum mechanics.For complete information on the specific topic in quantum physics, see Matrix mechanics.
Werner Heisenberg contributed to science at a point when the old quantum physics was discovering a field littered with more and more stumbling blocks. He decided that quantum physics had to be re-thought from the ground up. In doing so he excised several items that were grounded in classical physics and its modeling of the macro world. Heisenberg determined to base his quantum mechanics "exclusively upon relationships between quantities that in principle are observable." By so doing he constructed an entryway to matrix mechanics.
He observed that one could not then use any statements about such things as "the position and period of revolution of the electron." Rather, to make true progress in understanding the radiation of the simplest case, the radiation of excited hydrogen atoms, one had measurements only of the frequencies and the intensities of the hydrogen bright-line spectrum to work with.
In classical physics, the intensity of each frequency of light produced in a radiating system is equal to the square of the amplitude of the radiation at that frequency, so attention next fell on amplitudes. The classical equations that Heisenberg hoped to use to form quantum theoretical equations would first yield the amplitudes, and in classical physics one could compute the intensities simply by squaring the amplitudes. But Heisenberg saw that "the simplest and most natural assumption would be" to follow the lead provided by recent work in computing light dispersion done by Kramers. The work he had done assisting Kramers in the previous year now gave him an important clue about how to model what happened to excited hydrogen gas when it radiated light and what happened when incoming radiation of one frequency excited atoms in a dispersive medium and then the energy delivered by the incoming light was re-radiated — sometimes at the original frequency but often at two lower frequencies the sum of which equalled the original frequency. According to their model, an electron that had been driven to a higher energy state by accepting the energy of an incoming photon might return in one step to its equilibrium position, re-radiating a photon of the same frequency, or it might return in more than one step, radiating one photon for each step in its return to its equilibrium state. Because of the way factors cancel out in deriving the new equation based on these considerations, the result turns out to be relatively simple.Langer correction
The Langer correction is a correction when the WKB approximation method is applied to three-dimensional problems with spherical symmetry.
When applying WKB approximation method to the radial Schrödinger equation
where the effective potential is given by
the eigenenergies and the wave function behaviour obtained are different from the real solution.
In 1937, Rudolph E. Langer suggested a correction
which is known as Langer correction or Langer replacement. This is equivalent to inserting a 1/4 constant factor whenever ℓ(ℓ + 1) appears. Heuristically, it is said that this factor arises because the range of the radial Schrödinger equation is restricted from 0 to infinity, as opposed to the entire real line.
By such a changing of constant term in the effective potential, the results obtained by WKB approximation reproduces the exact spectrum for many potentials.
That the Langer replacement is correct follows from the WKB calculation of the Coulomb eigenvalues with this replacement which reproduces the well known result. An even more convincing calculation is the derivation of Regge trajectories (and hence eigenvalues) of the radial Schrödinger equation with Yukawa potential by both a perturbation method (with the old factor) and independently the derivation by the WKB method (with Langer replacement)-- in both cases even to higher orders. For the perturbation calculation see Müller-Kirsten and for the WKB calculation Boukema.List of important publications in chemistry
This is a list of important publications in chemistry, organized by field.Some factors that correlate with publication notability include:
Topic creator – A publication that created a new topic.
Breakthrough – A publication that changed scientific knowledge significantly.
Influence – A publication which has significantly influenced the world or has had a massive impact on the teaching of chemistry.Mathieu function
In mathematics, the Mathieu functions are certain special functions useful for treating a variety of problems in applied mathematics, including:
vibrating elliptical drumheads,
quadrupole mass analyzers and quadrupole ion traps for mass spectrometry
wave motion in periodic media, such as ultracold atoms in an optical lattice
the phenomenon of parametric resonance in forced oscillators,
exact plane wave solutions in general relativity,
eigenfunctions of the quantum pendulum Hamiltonian,
the Stark effect for a rotating electric dipole,
in general, the solution of differential equations that are separable in elliptic cylindrical coordinates,
eigenfunctions of a Josephson junction.They were introduced by Émile Léonard Mathieu (1868) in the context of the first problem.Michelle Francl
Michelle M. Francl is an American chemist. Francl is a professor of chemistry, and has taught physical chemistry, general chemistry and mathematical modeling at Bryn Mawr College since 1986.Francl is noted for developing new methodology in computational chemistry, including the 6-31G* basis set for Na to Ar and electrostatic potential charges.
She received a Ph.D. from the University of California, Irvine in 1983
On a list of the 1000 most cited chemists, Francl is a member of the editorial board for the Journal of Molecular Graphics and Modelling, active in the American Chemical Society and the author of The Survival Guide for Physical Chemistry. In 1994, she was awarded the Christian R. and Mary F. Lindback Award by Bryn Mawr College for excellence in teaching.Francl's podcast, "Introduction to Quantum Mechanics," broke into the iTunes Top 100 in October 2005, and currently writes for Nature Chemistry.Orbital motion (quantum)
Quantum orbital motion involves the quantum mechanical motion of rigid particles (such as electrons) about some other mass, or about themselves. Typically, orbital motion in classical motion is characterized by orbital angular momentum (the orbital motion of the center of mass) and spin, which is the motion about the center of mass. In quantum mechanics, there are analogous forms of spin and angular momentum, however they differ fundamentally from the models of classical bodies. For example, an electron (one of the main particles of concern in quantum mechanics) exhibits very quantum mechanical behavior in its motion around the nucleus of an atom which cannot be explained by classical mechanics.Quantum
In physics, a quantum (plural: quanta) is the minimum amount of any physical entity (physical property) involved in an interaction. The fundamental notion that a physical property may be "quantized" is referred to as "the hypothesis of quantization". This means that the magnitude of the physical property can take on only discrete values consisting of integer multiples of one quantum.
For example, a photon is a single quantum of light (or of any other form of electromagnetic radiation). Similarly, the energy of an electron bound within an atom is quantized and can exist only in certain discrete values. (Indeed, atoms and matter in general are stable because electrons can exist only at discrete energy levels within an atom.) Quantization is one of the foundations of the much broader physics of quantum mechanics. Quantization of energy and its influence on how energy and matter interact (quantum electrodynamics) is part of the fundamental framework for understanding and describing nature.Quantum metamaterial
Quantum metamaterials extend the science of metamaterials to the quantum level. They can control electromagnetic radiation by applying the rules of quantum mechanics. In the broad sense, a quantum metamaterial is a metamaterial in which certain quantum properties of the medium must be taken into account and whose behaviour is thus described by both Maxwell's equations and the Schrödinger equation. Its behaviour reflects the existence of both EM waves and matter waves. The constituents can be at nanoscopic or microscopic scales, depending on the frequency range (e.g., optical or microwave).In a more strict approach, a quantum metamaterial should demonstrate coherent quantum dynamics. Such a system is essentially a spatially extended controllable quantum object that allows additional ways of controlling the propagation of electromagnetic waves.Quantum metamaterials can be narrowly defined as optical media that:
Are composed of quantum coherent unit elements with engineered parameters;
Exhibit controllable quantum states of these elements;
Maintain quantum coherence for longer than the traversal time of a relevant electromagnetic signal.Rabi cycle
In physics, the Rabi cycle (or Rabi flop) is the cyclic behaviour of a two-level quantum system in the presence of an oscillatory driving field. A great variety of physical processes belonging to the areas of quantum computing, condensed matter, atomic and molecular physics, and nuclear and particle physics can be conveniently studied in terms of two-level quantum mechanical systems, and exhibit Rabi flopping when coupled to an oscillatory driving field. The effect is important in quantum optics, magnetic resonance and quantum computing, and is named after Isidor Isaac Rabi.
A two-level system has two possible levels, and if they are not degenerate (i.e. equal energy), the system can become "excited" when it absorbs a quantum of energy. When an atom (or some other two-level system) is illuminated by a coherent beam of photons, it will cyclically absorb photons and re-emit them by stimulated emission. One such cycle is called a Rabi cycle and the inverse of its duration the Rabi frequency of the photon beam. The effect can be modeled using the Jaynes–Cummings model and the Bloch vector formalism.State space (physics)
In physics, a state space is an abstract space in which different "positions" represent, not literal locations, but rather states of some physical system. This makes it a type of phase space.
Specifically, in quantum mechanics a state space is a complex Hilbert space in which the possible instantaneous states of the system may be described by unit vectors. These state vectors, using Dirac's bra–ket notation, can often be treated like coordinate vectors and operated on using the rules of linear algebra. This Dirac formalism of quantum mechanics can replace calculation of complicated integrals with simpler vector operations.Transmission coefficient
The transmission coefficient is used in physics and electrical engineering when wave propagation in a medium containing discontinuities is considered. A transmission coefficient describes the amplitude, intensity, or total power of a transmitted wave relative to an incident wave.
Different fields have different definitions for the term.Variational principle
The variational principle is a scientific principle used within the calculus of variations, which develops general methods for finding functions which extremize the value of quantities that depend upon those functions. For example, to answer this question: "What is the shape of a chain suspended at both ends?" we can use the variational principle that the shape must minimize the gravitational potential energy.Wave function collapse
In quantum mechanics, wave function collapse is said to occur when a wave function—initially in a superposition of several eigenstates—appears to reduce to a single eigenstate due to interaction with the external world; this is called an "observation". It is the essence of measurement in quantum mechanics and connects the wave function with classical observables like position and momentum. Collapse is one of two processes by which quantum systems evolve in time; the other is continuous evolution via the Schrödinger equation. However, in this role, collapse is merely a black box for thermodynamically irreversible interaction with a classical environment. Calculations of quantum decoherence predict apparent wave function collapse when a superposition forms between the quantum system's states and the environment's states. Significantly, the combined wave function of the system and environment continue to obey the Schrödinger equation.In 1927, Werner Heisenberg used the idea of wave function reduction to explain quantum measurement. Nevertheless, it was debated, for if collapse were a fundamental physical phenomenon, rather than just the epiphenomenon of some other process, it would mean nature was fundamentally stochastic, i.e. nondeterministic, an undesirable property for a theory. This issue remained until quantum decoherence entered mainstream opinion after its reformulation in the 1980s. Decoherence explains the perception of wave function collapse in terms of interacting large- and small-scale quantum systems.Yukawa potential
In particle, atomic and condensed matter physics, a Yukawa potential (also called a screened Coulomb potential) is a potential of the form
where g is a magnitude scaling constant, i.e. is the amplitude of potential, m is the mass of the particle, r is the radial distance to the particle, and α is another scaling constant, so that is the range. The potential is monotone increasing in r and it is negative, implying the force is attractive. In the SI system, the unit of the Yukawa potential is (1/meters).
The Coulomb potential of electromagnetism is an example of a Yukawa potential with equal to 1 everywhere. This can be interpreted as saying that the photon mass m is equal to 0.
In interactions between a meson field and a fermion field, the constant g is equal to the gauge coupling constant between those fields. In the case of the nuclear force, the fermions would be a proton and another proton or a neutron.