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Chemistry 352

Heisenberg Uncertainty Principle

Uncertainty: limits on simultaneous knowledge

How “spread” in position links to “spread” in momentum (and energy/time).

In quantum mechanics, a particle’s state is described by a wavefunction \( \psi(x) \). Measurement results are not single values every time; instead they have a distribution. The uncertainty in an observable is quantified by the standard deviation:

\[ \Delta x = \sqrt{\langle x^2\rangle - \langle x\rangle^2}, \qquad \Delta p = \sqrt{\langle p^2\rangle - \langle p\rangle^2}. \]

The Heisenberg uncertainty principle states that no quantum state can make both position and momentum arbitrarily sharp at the same time:

\[ \Delta x\,\Delta p \ge \frac{\hbar}{2}, \qquad \text{where } \hbar=\frac{h}{2\pi}. \]

Intuition: a wave that is very localized in space (small \( \Delta x \)) must be built from many different wavelengths (many different momenta), which produces a larger \( \Delta p \). Conversely, a nearly single-wavelength wave (sharp momentum) spreads out in space.

A common “order of magnitude” estimate comes from rearranging the inequality: if you confine a particle to a region of size \( \Delta x \), then

\[ \Delta p \gtrsim \frac{\hbar}{2\,\Delta x}. \]

There is also an energy–time form (used as a guideline for lifetimes and linewidths):

\[ \Delta E\,\Delta t \gtrsim \frac{\hbar}{2}. \]

Big idea: uncertainty is not a flaw in instruments—it is a property of quantum states.

Origin of the Heisenberg Uncertainty Principle from Commutators

In quantum mechanics, physical observables are represented by linear operators acting on a system’s wavefunction. Unlike classical variables, these operators do not necessarily commute. The failure of certain operators to commute is the fundamental origin of the Heisenberg uncertainty principle.

For two observables \( A \) and \( B \), represented by Hermitian operators \( \hat{A} \) and \( \hat{B} \), the commutator is defined as

\[ [\hat{A}, \hat{B}] = \hat{A}\hat{B} - \hat{B}\hat{A}. \]

If the commutator vanishes, the operators share a common set of eigenstates, and the corresponding observables can be simultaneously measured with arbitrary precision. If the commutator is nonzero, such simultaneous precision is fundamentally impossible.

This incompatibility leads directly to a quantitative uncertainty relation. For any normalized quantum state, the standard deviations \( \Delta A \) and \( \Delta B \) satisfy

\[ \Delta A \, \Delta B \ge \frac{1}{2} \left| \langle [\hat{A}, \hat{B}] \rangle \right|. \]

This result follows from the Cauchy–Schwarz inequality applied to the states \( (\hat{A}-\langle A\rangle)\psi \) and \( (\hat{B}-\langle B\rangle)\psi \). It shows that quantum uncertainty is not due to experimental limitations, but instead arises from the mathematical structure of the theory itself.

The most familiar example involves the position and momentum operators. In one dimension,

\[ \hat{x} = x, \qquad \hat{p} = -i\hbar \frac{d}{dx}, \]

which satisfy the canonical commutation relation

\[ [\hat{x}, \hat{p}] = i\hbar. \]

Substituting this commutator into the general uncertainty relation gives

\[ \Delta x \, \Delta p \ge \frac{\hbar}{2}. \]

Thus, the position–momentum uncertainty principle arises directly from the non-commutativity of the corresponding operators.

Although Heisenberg originally motivated this principle using measurement-based thought experiments, the modern interpretation is more fundamental: uncertainty is a consequence of operator non-commutativity. The commutator provides a precise algebraic measure of the incompatibility of two observables, and the uncertainty principle expresses this incompatibility quantitatively.

Now it's your turn!

Example 1
Which inequality correctly states the Heisenberg uncertainty principle for position and momentum?
\( \Delta x\,\Delta p \ge \hbar/2 \) \( \Delta x + \Delta p \ge \hbar/2 \) \( \Delta x\,\Delta p \le \hbar/2 \) \( \Delta x\,\Delta p \ge h \)
Example 2
If you make \( \Delta x \) smaller, what must happen to the minimum possible \( \Delta p \)?
It decreases It stays the same It increases It becomes zero
Example 3
A particle is localized to \( \Delta x = 1.0\times10^{-10}\,\text{m} \). Using \( \Delta x\,\Delta p \ge \hbar/2 \), which is the best estimate for the minimum momentum uncertainty?
\( \approx 5\times10^{-25}\,\text{kg·m/s} \) \( \approx 5\times10^{-24}\,\text{kg·m/s} \) \( \approx 5\times10^{-15}\,\text{kg·m/s} \) \( \approx 5\times10^{-34}\,\text{kg·m/s} \) \( \approx 5\times10^{-10}\,\text{kg·m/s} \)

Key points (one glance)