There are numerous mathematically equivalent formulations of quantum mechanics. One of the oldest and most commonly used formulations is the transformation theory proposed by Cambridge theoretical physicist Paul Dirac, which unifies and generalizes the two earliest formulations of quantum mechanics, matrix mechanics (invented by Werner Heisenberg)[2] and wave mechanics (invented by Erwin Schrödinger).
In this formulation, the instantaneous state of a quantum system encodes the probabilities of its measurable properties, or "observables". Examples of observables include energy, position, momentum, and angular momentum. Observables can be either continuous (e.g., the position of a particle) or discrete (e.g., the energy of an electron bound to a hydrogen atom).
Generally, quantum mechanics does not assign definite values to observables. Instead, it makes predictions about probability distributions; that is, the probability of obtaining each of the possible outcomes from measuring an observable. Naturally, these probabilities will depend on the quantum state at the instant of the measurement. There are, however, certain states that are associated with a definite value of a particular observable. These are known as "eigenstates" of the observable ("eigen" can be roughly translated from German as inherent or as a characteristic). In the everyday world, it is natural and intuitive to think of everything being in an eigenstate of every observable. Everything appears to have a definite position, a definite momentum, and a definite time of occurrence. However, quantum mechanics does not pinpoint the exact values for the position or momentum of a certain particle in a given space in a finite time; rather, it only provides a range of probabilities of where that particle might be. Therefore, it became necessary to use different words for (a) the state of something having an uncertainty relation and (b) a state that has a definite value. The latter is called the "eigenstate" of the property being measured.
For example, consider a free particle. In quantum mechanics, there is wave-particle duality so the properties of the particle can be described as a wave. Therefore, its quantum state can be represented as a wave, of arbitrary shape and extending over all of space, called a wave function. The position and momentum of the particle are observables. The Uncertainty Principle of quantum mechanics states that both the position and the momentum cannot simultaneously be known with infinite precision at the same time. However, one can measure just the position alone of a moving free particle creating an eigenstate of position with a wavefunction that is very large at a particular position x, and almost zero everywhere else. If one performs a position measurement on such a wavefunction, the result x will be obtained with almost 100% probability. In other words, the position of the free particle will almost be known. This is called an eigenstate of position (mathematically more precise: a generalized eigenstate (eigendistribution) ). If the particle is in an eigenstate of position then its momentum is completely unknown. An eigenstate of momentum, on the other hand, has the form of a plane wave. It can be shown that the wavelength is equal to h/p, where h is Planck's constant and p is the momentum of the eigenstate. If the particle is in an eigenstate of momentum then its position is completely blurred out.
Usually, a system will not be in an eigenstate of whatever observable we are interested in. However, if one measures the observable, the wavefunction will instantaneously be an eigenstate (or generalized eigenstate) of that observable. This process is known as wavefunction collapse. It involves expanding the system under study to include the measurement device, so that a detailed quantum calculation would no longer be feasible and a classical description must be used. If one knows the corresponding wave function at the instant before the measurement, one will be able to compute the probability of collapsing into each of the possible eigenstates. For example, the free particle in the previous example will usually have a wavefunction that is a wave packet centered around some mean position x0, neither an eigenstate of position nor of momentum. When one measures the position of the particle, it is impossible to predict with certainty the result that we will obtain. It is probable, but not certain, that it will be near x0, where the amplitude of the wave function is large. After the measurement is performed, having obtained some result x, the wave function collapses into a position eigenstate centered at x.
Wave functions can change as time progresses. An equation known as the Schrödinger equation describes how wave functions change in time, a role similar to Newton's second law in classical mechanics. The Schrödinger equation, applied to the aforementioned example of the free particle, predicts that the center of a wave packet will move through space at a constant velocity, like a classical particle with no forces acting on it. However, the wave packet will also spread out as time progresses, which means that the position becomes more uncertain. This also has the effect of turning position eigenstates (which can be thought of as infinitely sharp wave packets) into broadened wave packets that are no longer position eigenstates.
Some wave functions produce probability distributions that are constant in time. Many systems that are treated dynamically in classical mechanics are described by such "static" wave functions. For example, a single electron in an unexcited atom is pictured classically as a particle moving in a circular trajectory around the atomic nucleus, whereas in quantum mechanics it is described by a static, spherically symmetric wavefunction surrounding the nucleus (Fig. 1). (Note that only the lowest angular momentum states, labeled s, are spherically symmetric).
The time evolution of wave functions is deterministic in the sense that, given a wavefunction at an initial time, it makes a definite prediction of what the wavefunction will be at any later time. During a measurement, the change of the wavefunction into another one is not deterministic, but rather unpredictable, i.e., random.
The probabilistic nature of quantum mechanics thus stems from the act of measurement. This is one of the most difficult aspects of quantum systems to understand. It was the central topic in the famous Bohr-Einstein debates, in which the two scientists attempted to clarify these fundamental principles by way of thought experiments. In the decades after the formulation of quantum mechanics, the question of what constitutes a "measurement" has been extensively studied. Interpretations of quantum mechanics have been formulated to do away with the concept of "wavefunction collapse"; see, for example, the relative state interpretation. The basic idea is that when a quantum system interacts with a measuring apparatus, their respective wavefunctions become entangled, so that the original quantum system ceases to exist as an independent entity. For details, see the article on measurement in quantum mechanics.
[edit] Mathematical formulation
Main article: Mathematical formulation of quantum mechanics
See also: Quantum logic
In the mathematically rigorous formulation of quantum mechanics, developed by Paul Dirac and John von Neumann, the possible states of a quantum mechanical system are represented by unit vectors (called "state vectors") residing in a complex separable Hilbert space (variously called the "state space" or the "associated Hilbert space" of the system) well defined up to a complex number of norm 1 (the phase factor). In other words, the possible states are points in the projectivization of a Hilbert space. The exact nature of this Hilbert space is dependent on the system; for example, the state space for position and momentum states is the space of square-integrable functions, while the state space for the spin of a single proton is just the product of two complex planes. Each observable is represented by a maximally-Hermitian (precisely: by a self-adjoint) linear operator acting on the state space. Each eigenstate of an observable corresponds to an eigenvector of the operator, and the associated eigenvalue corresponds to the value of the observable in that eigenstate. If the operator's spectrum is discrete, the observable can only attain those discrete eigenvalues.
The time evolution of a quantum state is described by the Schrödinger equation, in which the Hamiltonian, the operator corresponding to the total energy of the system, generates time evolution.
The inner product between two state vectors is a complex number known as a probability amplitude. During a measurement, the probability that a system collapses from a given initial state to a particular eigenstate is given by the square of the absolute value of the probability amplitudes between the initial and final states. The possible results of a measurement are the eigenvalues of the operator - which explains the choice of Hermitian operators, for which all the eigenvalues are real. We can find the probability distribution of an observable in a given state by computing the spectral decomposition of the corresponding operator. Heisenberg's uncertainty principle is represented by the statement that the operators corresponding to certain observables do not commute.
The Schrödinger equation acts on the entire probability amplitude, not merely its absolute value. Whereas the absolute value of the probability amplitude encodes information about probabilities, its phase encodes information about the interference between quantum states. This gives rise to the wave-like behavior of quantum states.
It turns out that analytic solutions of Schrödinger's equation are only available for a small number of model Hamiltonians, of which the quantum harmonic oscillator, the particle in a box, the hydrogen-molecular ion and the hydrogen atom are the most important representatives. Even the helium atom, which contains just one more electron than hydrogen, defies all attempts at a fully analytic treatment. There exist several techniques for generating approximate solutions. For instance, in the method known as perturbation theory one uses the analytic results for a simple quantum mechanical model to generate results for a more complicated model related to the simple model by, for example, the addition of a weak potential energy. Another method is the "semi-classical equation of motion" approach, which applies to systems for which quantum mechanics produces weak deviations from classical behavior. The deviations can be calculated based on the classical motion. This approach is important for the field of quantum chaos.
An alternative formulation of quantum mechanics is Feynman's path integral formulation, in which a quantum-mechanical amplitude is considered as a sum over histories between initial and final states; this is the quantum-mechanical counterpart of action principles in classical mechanics.
[edit] Interactions with other scientific theories
The fundamental rules of quantum mechanics are very broad. They assert that the state space of a system is a Hilbert space and the observables are Hermitian operators acting on that space, but do not tell us which Hilbert space or which operators, or if it even exists. These must be chosen appropriately in order to obtain a quantitative description of a quantum system. An important guide for making these choices is the correspondence principle, which states that the predictions of quantum mechanics reduce to those of classical physics when a system moves to higher energies or equivalently, larger quantum numbers. In other words, classic mechanics is simply a quantum mechanics of large systems. This "high energy" limit is known as the classical or correspondence limit. One can therefore start from an established classical model of a particular system, and attempt to guess the underlying quantum model that gives rise to the classical model in the correspondence limit
Unsolved problems in physics: In the correspondence limit of quantum mechanics: Is there a preferred interpretation of quantum mechanics? How does the quantum description of reality, which includes elements such as the superposition of states and wavefunction collapse, give rise to the reality we perceive?
When quantum mechanics was originally formulated, it was applied to models whose correspondence limit was non-relativistic classical mechanics. For instance, the well-known model of the quantum harmonic oscillator uses an explicitly non-relativistic expression for the kinetic energy of the oscillator, and is thus a quantum version of the classical harmonic oscillator.
Early attempts to merge quantum mechanics with special relativity involved the replacement of the Schrödinger equation with a covariant equation such as the Klein-Gordon equation or the Dirac equation. While these theories were successful in explaining many experimental results, they had certain unsatisfactory qualities stemming from their neglect of the relativistic creation and annihilation of particles. A fully relativistic quantum theory required the development of quantum field theory, which applies quantization to a field rather than a fixed set of particles. The first complete quantum field theory, quantum electrodynamics, provides a fully quantum description of the electromagnetic interaction.
The full apparatus of quantum field theory is often unnecessary for describing electrodynamic systems. A simpler approach, one employed since the inception of quantum mechanics, is to treat charged particles as quantum mechanical objects being acted on by a classical electromagnetic field. For example, the elementary quantum model of the hydrogen atom describes the electric field of the hydrogen atom using a classical -\frac{e^2}{4 \pi\ \epsilon_0\ } \frac{1}{r} Coulomb potential. This "semi-classical" approach fails if quantum fluctuations in the electromagnetic field play an important role, such as in the emission of photons by charged particles.
Quantum field theories for the strong nuclear force and the weak nuclear force have been developed. The quantum field theory of the strong nuclear force is called quantum chromodynamics, and describes the interactions of the subnuclear particles: quarks and gluons. The weak nuclear force and the electromagnetic force were unified, in their quantized forms, into a single quantum field theory known as electroweak theory.
It has proven difficult to construct quantum models of gravity, the remaining fundamental force. Semi-classical approximations are workable, and have led to predictions such as Hawking radiation. However, the formulation of a complete theory of quantum gravity is hindered by apparent incompatibilities between general relativity, the most accurate theory of gravity currently known, and some of the fundamental assumptions of quantum theory. The resolution of these incompatibilities is an area of active research, and theories such as string theory are among the possible candidates for a future theory of quantum gravity.
[edit] Derivation of quantization
The particle in a 1-dimensional potential energy box is the most simple example where restraints lead to the quantization of energy levels. The box is defined as zero potential energy inside a certain interval and infinite everywhere outside that interval. For the 1-dimensional case in the x direction, the time-independent Schrödinger equation can be written as[3]:
- \frac {\hbar ^2}{2m} \frac {d ^2 \psi}{dx^2} = E \psi.
The general solutions are:
\psi = A e^{ikx} + B e ^{-ikx} \;\;\;\;\;\; E = \frac{k^2 \hbar^2}{2m}
\psi = C \sin kx + D \cos kx \; (exponential rewrite)
The presence of the walls of the box restricts the acceptable solutions to the wavefunction. At each wall :
\psi = 0 \; \mathrm{at} \;\; x = 0,\; x = L
Consider x = 0
* sin 0 = 0, cos 0 = 1. To satisfy \psi = 0 \; D = 0 (cos term is removed)
Now Consider: \psi = C \sin kx \;
* at X = L, \psi = C \sin kL \;
* If C = 0 then \psi =0 \; for all x and would conflict with Born interpretation
* therefore sin kL must be satisfied by
kL = n \pi \;\;\;\; n = 1,2,3,4,5 \;