Quantum mechanics was successful at describing non-relativistic systems with fixed numbers of particles, but a new framework was needed to describe systems in which particles can be created or destroyed, for example, the electromagnetic field, considered as a collection of photons. It was eventually realized that
special relativity was inconsistent with single-particle quantum mechanics, so that all particles are now described relativistically by
quantum fields. When the canonical quantization procedure is applied to a field, such as the electromagnetic field, the classical
field variables become
quantum operators. Thus, the normal modes comprising the amplitude of the field are simple oscillators, each of which is
quantized in standard first quantization, above, without ambiguity. The resulting quanta are identified with individual particles or excitations. For example, the quanta of the electromagnetic field are identified with photons. Unlike first quantization, conventional second quantization is completely unambiguous, in effect a
functor, since the constituent set of its oscillators are quantized unambiguously. Historically, quantizing the classical theory of a single particle gave rise to a wavefunction. The classical equations of motion of a field are typically identical in form to the (quantum) equations for the wave-function of
one of its quanta. For example, the
Klein–Gordon equation is the classical equation of motion for a free scalar field, but also the quantum equation for a scalar particle wave-function. This meant that quantizing a field
appeared to be similar to quantizing a theory that was already quantized, leading to the fanciful term
second quantization in the early literature, which is still used to describe field quantization, even though the modern interpretation detailed is different. One drawback to canonical quantization for a relativistic field is that by relying on the Hamiltonian to determine time dependence,
relativistic invariance is no longer manifest. Thus it is necessary to check that
relativistic invariance is not lost. Alternatively, the
Feynman integral approach is available for quantizing relativistic fields, and is manifestly invariant. For non-relativistic field theories, such as those used in
condensed matter physics, Lorentz invariance is not an issue.
Field operators Quantum mechanically, the variables of a field (such as the field's amplitude at a given point) are represented by operators on a
Hilbert space. In general, all observables are constructed as operators on the Hilbert space, and the time-evolution of the operators is governed by the
Hamiltonian, which must be a
positive operator. A state |0\rangle annihilated by the Hamiltonian must be identified as the
vacuum state, which is the basis for building all other states. In a non-interacting (free) field theory, the vacuum is normally identified as a state containing zero particles. In a theory with interacting particles, identifying the vacuum is more subtle, due to
vacuum polarization, which implies that the physical vacuum in quantum field theory is never really empty. For further elaboration, see the articles on
the quantum mechanical vacuum and
the vacuum of quantum chromodynamics. The details of the canonical quantization depend on the field being quantized, and whether it is free or interacting.
Real scalar field A
scalar field theory provides a good example of the canonical quantization procedure. Classically, a scalar field is a collection of an infinity of
oscillator normal modes. It suffices to consider a 1+1-dimensional space-time \mathbb{R} \times S_1, in which the spatial direction is
compactified to a circle of circumference 2, rendering the momenta discrete. The classical
Lagrangian density describes an
infinity of coupled harmonic oscillators, labelled by which is now a
label (and not the displacement dynamical variable to be quantized), denoted by the classical field , \mathcal{L}(\phi) = \tfrac{1}{2}(\partial_t \phi)^2 - \tfrac{1}{2}(\partial_x \phi)^2 - \tfrac{1}{2} m^2\phi^2 - V(\phi), where is a potential term, often taken to be a polynomial or monomial of degree 3 or higher. The action functional is S(\phi) = \int \mathcal{L}(\phi) dx dt = \int L(\phi, \partial_t\phi) dt \, .The canonical momentum obtained via the
Legendre transformation using the action is \pi = \partial_t\phi, and the classical
Hamiltonian is found to be H(\phi,\pi) = \int dx \left[\tfrac{1}{2} \pi^2 + \tfrac{1}{2} (\partial_x \phi)^2 + \tfrac{1}{2} m^2 \phi^2 + V(\phi)\right]. Canonical quantization treats the variables and as operators with
canonical commutation relations at time = 0, given by [\phi(x),\phi(y)] = 0, \ \ [\pi(x), \pi(y)] = 0, \ \ [\phi(x),\pi(y)] = i\hbar \delta(x-y). Operators constructed from and can then formally be defined at other times via the time-evolution generated by the Hamiltonian, \mathcal{O}(t) = e^{itH} \mathcal{O} e^{-itH}. However, since and no longer commute, this expression is ambiguous at the quantum level. The problem is to construct a representation of the relevant operators \mathcal{O} on a
Hilbert space \mathcal{H} and to construct a positive operator as a
quantum operator on this Hilbert space in such a way that it gives this evolution for the operators \mathcal{O} as given by the preceding equation, and to show that \mathcal{H} contains a vacuum state |0\rangle on which has zero eigenvalue. In practice, this construction is a difficult problem for interacting field theories, and has been solved completely only in a few simple cases via the methods of
constructive quantum field theory. Many of these issues can be sidestepped using the Feynman integral as described for a particular in the article on
scalar field theory. In the case of a free field, with , the quantization procedure is relatively straightforward. It is convenient to
Fourier transform the fields, so that \phi_k = \int \phi(x) e^{-ikx} dx, \ \ \pi_k = \int \pi(x) e^{-ikx} dx. The reality of the fields implies that \phi_{-k} = \phi_k^\dagger, ~~~ \pi_{-k} = \pi_k^\dagger .The classical Hamiltonian may be expanded in Fourier modes as H=\frac{1}{2}\sum_{k=-\infty}^{\infty}\left[\pi_k \pi_k^\dagger + \omega_k^2\phi_k\phi_k^\dagger\right], where \omega_k = \sqrt{k^2+m^2}. This Hamiltonian is thus recognizable as an infinite sum of classical
normal mode oscillator excitations , each one of which is quantized in the
standard manner, so the free quantum Hamiltonian looks identical. It is the s that have become operators obeying the standard commutation relations, , with all others vanishing. The collective Hilbert space of all these oscillators is thus constructed using creation and annihilation operators constructed from these modes, a_k = \frac{1}{\sqrt{2\hbar\omega_k}}\left(\omega_k\phi_k + i\pi_k\right), \ \ a_k^\dagger = \frac{1}{\sqrt{2\hbar\omega_k}}\left(\omega_k\phi_k^\dagger - i\pi_k^\dagger\right), for which for all , with all other commutators vanishing. The vacuum |0\rangle is taken to be annihilated by all of the , and \mathcal{H} is the Hilbert space constructed by applying any combination of the infinite collection of creation operators † to |0\rangle. This Hilbert space is called
Fock space. For each , this construction is identical to a
quantum harmonic oscillator. The quantum field is an infinite array of quantum oscillators. The quantum Hamiltonian then amounts to H = \sum_{k=-\infty}^{\infty} \hbar\omega_k a_k^\dagger a_k = \sum_{k=-\infty}^{\infty} \hbar\omega_k N_k ,where may be interpreted as the
number operator giving the
number of particles in a state with momentum . This Hamiltonian differs from the previous expression by the subtraction of the zero-point energy of each harmonic oscillator. This satisfies the condition that must annihilate the vacuum, without affecting the time-evolution of operators via the above exponentiation operation. This subtraction of the
zero-point energy may be considered to be a resolution of the quantum operator ordering ambiguity, since it is equivalent to requiring that
all creation operators appear to the left of annihilation operators in the expansion of the Hamiltonian. This procedure is known as
Wick ordering or
normal ordering.
Other fields All other fields can be quantized by a generalization of this procedure. Vector or tensor fields simply have more components, and independent creation and destruction operators must be introduced for each independent component. If a field has any
internal symmetry, then creation and destruction operators must be introduced for each component of the field related to this symmetry as well. If there is a
gauge symmetry, then the number of independent components of the field must be carefully analyzed to avoid over-counting equivalent configurations, and
gauge-fixing may be applied if needed. It turns out that commutation relations are useful only for quantizing
bosons, for which the occupancy number of any state is unlimited. To quantize
fermions, which satisfy the
Pauli exclusion principle, anti-commutators are needed. These are defined by {{math|{
A,
B}
AB +
BA}}. When quantizing fermions, the fields are expanded in creation and annihilation operators, , , which satisfy \{\theta_k,\theta_l^\dagger\} = \delta_{kl}, \ \ \{\theta_k, \theta_l\} = 0, \ \ \{\theta_k^\dagger, \theta_l^\dagger\} = 0. The states are constructed on a vacuum |0\rangle annihilated by the , and the
Fock space is built by applying all products of creation operators to . Pauli's exclusion principle is satisfied, because (\theta_k^\dagger)^2|0\rangle = 0, by virtue of the anti-commutation relations.
Condensates The construction of the scalar field states above assumed that the potential was minimized at = 0, so that the vacuum minimizing the Hamiltonian satisfies , indicating that the
vacuum expectation value (VEV) of the field is zero. In cases involving
spontaneous symmetry breaking, it is possible to have a non-zero VEV, because the potential is minimized for a value = . This occurs for example, if with and , for which the minimum energy is found at . The value of in one of these vacua may be considered as
condensate of the field . Canonical quantization then can be carried out for the
shifted field , and particle states with respect to the shifted vacuum are defined by quantizing the shifted field. This construction is utilized in the
Higgs mechanism in the
Standard Model of
particle physics. == Mathematical quantization ==