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Chemistry · Glossary

What is Operator, eigenfunction, eigenvalue?

Also known as: operator · eigenfunction · eigenvalue

Definition 1.1 University Chemistry — Year 3 · Chapter 1 — Quantum Mechanics for Chemists: Model Systems

An operator A^\hat A is a rule that turns a function into another function: A^f=g\hat A f = g. It is linear if A^(λf+μg)=λA^f+μA^g\hat A(\lambda f + \mu g) = \lambda\hat Af + \mu\hat Ag. A non-zero function ff such that A^f=af\hat Af = a f for a number aa is an eigenfunction of A^\hat A, and aa is the corresponding eigenvalue.

Examples

Example 1.2 (Two operators of position and momentum)

In one dimension the position operator multiplies by xx, x^f=xf\hat x f = xf, and the momentum operator differentiates, p^f=−iℏ  ⁣df/ ⁣dx\hat p f = -\iu\hbar\, \dd f/\dd x, with ℏ=h/2π\hbar = h/2\pi. The function eikx\eu^{\iu kx} is an eigenfunction of p^\hat p with eigenvalue ℏk\hbar k: a wave of wavelength λ=2π/k\lambda = 2\pi/k has momentum h/λh/\lambda, de Broglie’s relation. The function sin⁡kx\sin kx is not an eigenfunction of p^\hat p (its derivative is a cosine), but it is one of p^2=−ℏ2  ⁣d2/ ⁣dx2\hat p^2 = -\hbar^2\,\dd^2/\dd x^2, with eigenvalue ℏ2k2\hbar^2k^2.

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