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Chemistry 352

Expectation Values

Expectation values (what you "expect" to measure)

How to compute average measurement outcomes from a wave function.

In quantum mechanics, each measurable quantity (position, momentum, energy, etc.) is represented by an operator \( \hat{A} \). If the particle is in the normalized state \( \psi(x) \), expectation value (average over many identical measurements) is

\[ \langle A \rangle = \int \psi^*(x)\,\hat{A}\,\psi(x)\,dx. \]

For a particle in a 1D infinite box from x=0 to x=L, the integral runs over the box:

\[ \langle A \rangle = \int_{0}^{L} \psi^*(x)\,\hat{A}\,\psi(x)\,dx. \]

Two very common operators are:

For the particle-in-a-box stationary states, \( \psi_n(x)=\sqrt{\frac{2}{L}}\sin\!\left(\frac{n\pi x}{L}\right) \) (with n=1,2,3,\dots), symmetry of the standing wave about x=L/2 gives a simple result:

\[ \langle x\rangle=\frac{L}{2}, \qquad \langle p\rangle=0. \]

Variance

A useful "spread" measure is the variance \( (\Delta x)^2=\langle x^2\rangle-\langle x\rangle^2 \). For box states one finds

\[ \langle x^2\rangle = L^2\left(\frac{1}{3}-\frac{1}{2n^2\pi^2}\right), \qquad (\Delta x)^2 = L^2\left(\frac{1}{12}-\frac{1}{2n^2\pi^2}\right). \]

Big idea: expectation values come from \( \psi^*\,\hat{A}\,\psi \). The "probability density" is \( |\psi(x)|^2 \). The variance can be calculated from \( (\Delta a)^2=\langle a^2\rangle-\langle a\rangle^2 \).

Now it's your turn!

Example 1
For any particle in a 1D box (0 to L) in a stationary state, what is the expectation value of position, ⟨x⟩?
0
L/4
L/2
L
Example 2
Which operator corresponds to the x-component of momentum in 1D?
\(x\) \(-i\hbar\,\frac{d}{dx}\) \(i\hbar\,\frac{d}{dx}\) \(-\frac{\hbar^2}{2m}\,\frac{d^2}{dx^2}\)
Example 3
For the particle-in-a-box state ψn, which expression equals ⟨x2⟩?
\( \frac{L^2}{12} \) \( \frac{L^2}{3} \) \( L^2\left(\frac{1}{3}-\frac{1}{2n^2\pi^2}\right) \) \( L^2\left(\frac{1}{12}-\frac{1}{2n^2\pi^2}\right) \) \( \frac{L^2}{4} \)

Key points (one glance)