Perturbation theory (quantum mechanics)
In quantum mechanics, perturbation theory is a set of approximation schemes directly related to mathematical perturbation for describing a complicated quantum system in terms of a simpler, known system. The idea is to start with a simple system for which a mathematical solution is known and add an additional "perturbing" Hamiltonian representing a weak disturbance to the known system to the original Hamiltonian of the known system. If the disturbance is small, the new energy levels and eigenstates of the perturbed system can be expressed as "corrections" to the known energy levels and eigenstates of the simpler system. These corrections can be made at progressively smaller orders of magnitude until an n-th order that is so small a correction that it is negligible to the accuracy of the approximation.
Approximate Hamiltonians
Perturbation theory is an important tool for describing real quantum systems, as it turns out to be very difficult to find exact solutions to the Schrödinger equation for Hamiltonians of even moderate complexity. The Hamiltonians to which we know exact solutions, such as the hydrogen atom, the quantum harmonic oscillator and the particle in a box, are too idealized to adequately describe most systems. Using perturbation theory, we can use the known solutions of these simple Hamiltonians to generate solutions for a range of more complicated systems.Applying perturbation theory
Perturbation theory is applicable if the problem at hand cannot be solved exactly, but can be formulated by adding a "small" term to the mathematical description of the exactly solvable problem.For example, by adding a perturbative electric potential to the quantum mechanical model of the hydrogen atom, tiny shifts in the spectral lines of hydrogen caused by the presence of an electric field can be calculated. This is only approximate because the sum of a Coulomb potential with a linear potential is unstable although the tunneling time is very long. This instability shows up as a broadening of the energy spectrum lines, which perturbation theory fails to reproduce entirely.
The expressions produced by perturbation theory are not exact, but they can lead to accurate results as long as the expansion parameter, say, is very small. Typically, the results are expressed in terms of finite power series in that seem to converge to the exact values when summed to higher order. After a certain order however, the results become increasingly worse since the series are usually divergent. There exist ways to convert them into convergent series, which can be evaluated for large-expansion parameters, most efficiently by the variational method. In practice, convergent perturbation expansions often converge slowly while divergent perturbation expansions sometimes give good results, c.f. the exact solution, at lower order.
In the theory of quantum electrodynamics, in which the electron–photon interaction is treated perturbatively, the calculation of the electron's magnetic moment has been found to agree with experiment to eleven decimal places. In QED and other quantum field theories, special calculation techniques known as Feynman diagrams are used to systematically sum the power series terms.
Limitations
Large perturbations
Under some circumstances, perturbation theory is an invalid approach to take. This happens when the system we wish to describe cannot be described by a small perturbation imposed on some simple system. In quantum chromodynamics, for instance, the interaction of quarks with the gluon field cannot be treated perturbatively at low energies because the coupling constant becomes too large, violating the requirement that corrections must be small.Non-adiabatic states
Perturbation theory also fails to describe states that are not generated adiabatically from the "free model", including bound states and various collective phenomena such as solitons. Imagine, for example, that we have a system of free particles, to which an attractive interaction is introduced. Depending on the form of the interaction, this may create an entirely new set of eigenstates corresponding to groups of particles bound to one another. An example of this phenomenon may be found in conventional superconductivity, in which the phonon-mediated attraction between conduction electrons leads to the formation of correlated electron pairs known as Cooper pairs. When faced with such systems, one usually turns to other approximation schemes, such as the variational method and the WKB approximation. This is because there is no analogue of a bound particle in the unperturbed model and the energy of a soliton typically goes as the inverse of the expansion parameter. However, if we "integrate" over the solitonic phenomena, the nonperturbative corrections in this case will be tiny; of the order of or in the perturbation parameter. Perturbation theory can only detect solutions "close" to the unperturbed solution, even if there are other solutions for which the perturbative expansion is not valid.Difficult computations
The problem of non-perturbative systems has been somewhat alleviated by the advent of modern computers. It has become practical to obtain numerical non-perturbative solutions for certain problems, using methods such as density functional theory. These advances have been of particular benefit to the field of quantum chemistry. Computers have also been used to carry out perturbation theory calculations to extraordinarily high levels of precision, which has proven important in particle physics for generating theoretical results that can be compared with experiment.Time-independent perturbation theory
Time-independent perturbation theory is one of two categories of perturbation theory, the other being time-dependent perturbation. In time-independent perturbation theory, the perturbation Hamiltonian is static. Time-independent perturbation theory was presented by Erwin Schrödinger in a 1926 paper, shortly after he produced his theories in wave mechanics. In this paper Schrödinger referred to earlier work of Lord Rayleigh, who investigated harmonic vibrations of a string perturbed by small inhomogeneities. This is why this perturbation theory is often referred to as Rayleigh–Schrödinger perturbation theory. Time-independent perturbation theory can itself be separated into non-degenerate and degenerate perturbation theory.Non-degenerate perturbation theory
First order corrections
The process begins with an unperturbed Hamiltonian, which is assumed to have no time dependence. It has known energy levels and eigenstates, arising from the time-independent Schrödinger equation:For simplicity, it is assumed that the energies are discrete. The superscripts denote that these quantities are associated with the unperturbed system. Note the use of bra–ket notation.
A perturbation is then introduced to the Hamiltonian. Let be a Hamiltonian representing a weak physical disturbance, such as a potential energy produced by an external field. Thus, is formally a Hermitian operator. Let be a dimensionless parameter that can take on values ranging continuously from 0 to 1. The perturbed Hamiltonian is:
The energy levels and eigenstates of the perturbed Hamiltonian are again given by the time-independent Schrödinger equation,
The objective is to express and in terms of the energy levels and eigenstates of the old Hamiltonian. If the perturbation is sufficiently weak, they can be written as a power series in,
where
When, these reduce to the unperturbed values, which are the first term in each series. Since the perturbation is weak, the energy levels and eigenstates should not deviate too much from their unperturbed values, and the terms should rapidly become smaller as the order is increased.
Substituting the power series expansion into the Schrödinger equation produces:
Expanding this equation and comparing coefficients of each power of results in an infinite series of simultaneous equations. The zeroth-order equation is simply the Schrödinger equation for the unperturbed system,
The first-order equation is
Operating through by, the first term on the left-hand side cancels the first term on the right-hand side.. This leads to the first-order energy shift,
This is simply the expectation value of the perturbation Hamiltonian while the system is in the unperturbed eigenstate.
This result can be interpreted in the following way: supposing that the perturbation is applied, but the system is kept in the quantum state, which is a valid quantum state though no longer an energy eigenstate. The perturbation causes the average energy of this state to increase by. However, the true energy shift is slightly different, because the perturbed eigenstate is not exactly the same as. These further shifts are given by the second and higher order corrections to the energy.
Before corrections to the energy eigenstate are computed, the issue of normalization must be addressed. Supposing that
but perturbation theory also assumes that.
Then at first order in, the following must be true:
Since the overall phase is not determined in quantum mechanics, without loss of generality, in time-independent theory it can be assumed that is purely real. Therefore,
leading to
To obtain the first-order correction to the energy eigenstate, the expression for the first-order energy correction is inserted back into the result shown above, equating the first-order coefficients of.
The first-order correction to the energy eigenstate can also be obtained through the following considerations. By using the resolution of the identity:
where the are in the orthogonal complement of, i.e., the other eigenvectors.
The first-order equation may thus be expressed as
Suppose that the zeroth-order energy level is not degenerate, i.e. that there is no eigenstate of in the orthogonal complement of with the energy. After renaming the summation dummy index above as, any can be chosen and multiplying the first-order equation through by gives
The above is, by definition, the component of the first-order correction along. Thus, in the basis, can be expressed as:
The first-order change in the -th energy eigenstate has a contribution from each of the other energy eigenstates. Each term is proportional to the matrix element, which is a measure of how much the perturbation mixes eigenstate with eigenstate ; it is also inversely proportional to the energy difference between eigenstates and, which means that the perturbation deforms the eigenstate to a greater extent if there are more eigenstates at nearby energies. The expression is singular if any of these states have the same energy as state, which is why it was assumed that there is no degeneracy. The above formula for the perturbed eigenstates also implies that the perturbation theory can be legitimately used only when the absolute magnitude of the matrix elements of the perturbation is small compared with the corresponding differences in the unperturbed energy levels, i.e.,