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 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 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.

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.

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.

For example, by adding a perturbative electric 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 (has no true bound states) although the tunneling time (decay rate) is very long. This instability shows up as a broadening of the energy spectrum lines, which perturbation theory fails to reproduce entirely.

...
Wikipedia