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 one. 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 system. If the disturbance is not too large, the various physical quantities associated with the perturbed system (e.g. its energy levels and eigenstates) can, from considerations of continuity, be expressed as ‘corrections’ to those of the simple system. These corrections, being ‘small’ compared to the size of the quantities themselves, can be calculated using approximate methods such as asymptotic series. The complicated system can therefore be studied based on knowledge of the simpler one.
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. For example, by adding a perturbativeelectric potential to the quantum mechanical model of the hydrogen atom, we can calculate the tiny shifts in the spectral lines of hydrogen caused by the presence of an electric field (the Stark effect). This is only approximate because the sum of a Coulomb potential with a linear potential is unstable although the tunneling time (decay rate) is very long. This shows up as a broadening of the energy spectrum lines, something which perturbation theory fails to reproduce entirely.
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. When faced with such systems, one usually turns to other approximation schemes, such as the variational method and the WKB approximation.
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.