Particle in a box The particle in a one-dimensional potential energy box is the most mathematically simple example where restraints lead to the quantization of energy levels. The box is defined as having zero potential energy
inside a certain region and infinite potential energy
outside. For the one-dimensional case in the x direction, the time-independent Schrödinger equation may be written - \frac {\hbar^2\vphantom{\psi}}{2m\vphantom{x^2}} \frac {d^2 \psi}{dx^2} = E \psi. With the differential operator defined by \hat{p}_x = -i\hbar\frac{d}{dx} the previous equation is evocative of the
classic kinetic energy analogue, \frac{1}{2m} \hat{p}_x^2 = E, with state \psi in this case having energy E coincident with the kinetic energy of the particle. The general solutions of the Schrödinger equation for the particle in a box are \psi(x) = A e^{ikx} + B e ^{-ikx} \qquad\qquad E = \frac{\hbar^2 k^2}{2m} or, from
Euler's formula, \psi(x) = C \sin(kx) + D \cos(kx). The infinite potential walls of the box determine the values of C, D, and k at x=0 and x=L where \psi must be zero. Thus, at x=0, \psi(0) = 0 = C\sin(0) + D\cos(0) = D and D=0. At x=L, \psi(L) = 0 = C\sin(kL), in which C cannot be zero as this would conflict with the postulate that \psi has norm 1. Therefore, since \sin(kL)=0, kL must be an integer multiple of \pi, k = \frac{n\pi}{L}\qquad\qquad n=1,2,3,\ldots. This constraint on k implies a constraint on the energy levels, yielding E_n = \frac{\hbar^2 \pi^2 n^2}{2mL^2} = \frac{n^2h^2}{8mL^2}. A
finite potential well is the generalization of the infinite potential well problem to potential wells having finite depth. The finite potential well problem is mathematically more complicated than the infinite particle-in-a-box problem as the wave function is not pinned to zero at the walls of the well. Instead, the wave function must satisfy more complicated mathematical boundary conditions as it is nonzero in regions outside the well. Another related problem is that of the
rectangular potential barrier, which furnishes a model for the
quantum tunneling effect that plays an important role in the performance of modern technologies such as
flash memory and
scanning tunneling microscopy.
Harmonic oscillator in classical mechanics (A–B) and quantum mechanics (C–H). In (A–B), a ball, attached to a
spring, oscillates back and forth. (C–H) are six solutions to the Schrödinger Equation for this situation. The horizontal axis is position, the vertical axis is the real part (blue) or imaginary part (red) of the
wave function.
Stationary states, or energy eigenstates, which are solutions to the time-independent Schrödinger equation, are shown in C, D, E, F, but not G or H. The Schrödinger equation for this situation is E\psi = -\frac{\hbar^2}{2m\vphantom{x^2}}\frac{d^2}{d x^2}\psi + \frac{1}{2\vphantom{x^2}} m\omega^2 x^2\psi, where x is the displacement and \omega the angular frequency. Furthermore, it can be used to describe approximately a wide variety of other systems, including
vibrating atoms, molecules, and atoms or ions in lattices, and approximating other potentials near equilibrium points. It is also the
basis of perturbation methods in quantum mechanics. The solutions in position space are \psi_n(x) = \sqrt{\frac{1}{2^n\,n!}} \ \left(\frac{m\omega}{\pi \hbar}\right)^{1/4} \ e^{ - \frac{m\omega x^2}{2 \hbar}} \ \mathcal{H}_n\left(\sqrt{\frac{m\omega}{\hbar}} x \right), where n \in \{0, 1, 2, \ldots \}, and the functions \mathcal{H}_n are the
Hermite polynomials of order n . The solution set may be generated by \psi_n(x) = \frac{1}{\sqrt{n!}} \left( \sqrt{\frac{m \omega}{2 \hbar}} \right)^{n} \left( x - \frac{\hbar}{m \omega} \frac{d}{dx}\right)^n \left( \frac{m \omega}{\pi \hbar} \right)^{\frac{1}{4}} e^{\frac{-m \omega x^2}{2\hbar}}. The eigenvalues are E_n = \left(n + \frac{1}{2} \right) \hbar \omega. The case n = 0 is called the
ground state, its energy is called the
zero-point energy, and the wave function is a
Gaussian. The harmonic oscillator, like the particle in a box, illustrates the generic feature of the Schrödinger equation that the energies of bound eigenstates are discretized. In this case,
spherical polar coordinates are the most convenient. Thus, \psi(r,\theta,\varphi) = R(r) \ Y_\ell^m(\theta, \varphi) = R(r) \ \Theta(\theta) \ \Phi(\varphi), where are radial functions and Y^m_l (\theta, \varphi) are
spherical harmonics of degree \ell and order m . This is the only atom for which the Schrödinger equation has been solved exactly. Multi-electron atoms require approximate methods. The family of solutions are: \psi_{n\ell m}(r,\theta,\varphi) = \sqrt {\left ( \frac{2}{n a_0} \right )^3\frac{(n-\ell-1)!}{2n[(n+\ell)!]} } e^{- r/na_0} \left(\frac{2r}{na_0}\right)^\ell L_{n-\ell-1}^{2\ell+1}\left(\frac{2r}{na_0}\right) \cdot Y_{\ell}^m(\theta, \varphi ) where • a_0 = \frac{4 \pi \varepsilon_0 \hbar^2}{m_q q^2} is the
Bohr radius, • L_{n-\ell-1}^{2\ell+1}(\cdots) are the
generalized Laguerre polynomials of degree n - \ell - 1 , • n, \ell, m are the
principal,
azimuthal, and
magnetic quantum numbers respectively, which take the values n = 1, 2, 3, \dots, \ell = 0, 1, 2, \dots, n - 1, m = -\ell, \dots, \ell.
Approximate solutions It is typically not possible to solve the Schrödinger equation exactly for situations of physical interest. Accordingly, approximate solutions are obtained using techniques like
variational methods and
WKB approximation. It is also common to treat a problem of interest as a small modification to a problem that can be solved exactly, a method known as
perturbation theory. == Semiclassical limit ==