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⚗️Theoretical Chemistry Unit 3 Review

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3.3 Commutation relations and uncertainty principle

⚗️Theoretical Chemistry
Unit 3 Review

3.3 Commutation relations and uncertainty principle

Written by the Fiveable Content Team • Last updated September 2025
Written by the Fiveable Content Team • Last updated September 2025
⚗️Theoretical Chemistry
Unit & Topic Study Guides

Quantum mechanics introduces mind-bending concepts like commutation relations and the uncertainty principle. These ideas challenge our classical intuitions, revealing the fuzzy nature of reality at the atomic scale.

Commutators help us understand which properties we can measure together. The uncertainty principle shows there are fundamental limits to what we can know about particles. These ideas are key to grasping quantum weirdness.

Commutation Relations

Commutator and Observable Compatibility

  • The commutator is a mathematical operation that measures the difference between the product of two operators in two different orders, defined as $[A, B] = AB - BA$
  • When the commutator of two operators equals zero, $[A, B] = 0$, the operators are said to commute and the corresponding observables are compatible
    • Compatible observables can be measured simultaneously with arbitrary precision
    • Examples of compatible observables include the x-component of angular momentum ($L_x$) and the square of the total angular momentum ($L^2$)
  • Incompatible observables have a non-zero commutator, $[A, B] \neq 0$, meaning the operators do not commute
    • Incompatible observables cannot be measured simultaneously with arbitrary precision
    • Measuring one observable disturbs the system, affecting the measurement of the other observable
    • Examples of incompatible observables include position ($x$) and momentum ($p_x$), which have the commutator $[x, p_x] = i\hbar$

Heisenberg Uncertainty Principle

Position-Momentum and Energy-Time Uncertainty

  • The Heisenberg uncertainty principle states that the product of the uncertainties in the measurements of certain pairs of observables is always greater than or equal to a constant value
    • Mathematically, for position and momentum: $\Delta x \Delta p_x \geq \frac{\hbar}{2}$
    • For energy and time: $\Delta E \Delta t \geq \frac{\hbar}{2}$
  • The position-momentum uncertainty relation implies that the more precisely the position of a particle is measured, the less precisely its momentum can be determined, and vice versa
    • This is a consequence of the wave-particle duality of quantum mechanics
    • Example: An electron confined to a small region in space (small $\Delta x$) will have a large uncertainty in its momentum (large $\Delta p_x$)
  • The energy-time uncertainty relation states that the product of the uncertainties in energy and time is always greater than or equal to $\frac{\hbar}{2}$
    • This relation is often interpreted as the time required for a quantum system to evolve from one state to another is inversely proportional to the energy difference between the states
    • Example: A metastable state with a long lifetime (large $\Delta t$) will have a small uncertainty in its energy (small $\Delta E$)

Complementarity and Wave-Particle Duality

  • Complementarity is the principle that a quantum system can exhibit mutually exclusive properties, such as wave-like and particle-like behavior, depending on the experimental setup
    • These properties are complementary in the sense that the more one property is observed, the less the other property is observed
    • Example: In the double-slit experiment, observing which slit the particle passes through (particle-like behavior) destroys the interference pattern (wave-like behavior)
  • The Heisenberg uncertainty principle and complementarity are closely related to the wave-particle duality of quantum mechanics
    • The wave-particle duality states that quantum entities can exhibit both wave-like and particle-like properties
    • The uncertainty principle and complementarity provide a quantitative and qualitative understanding of the limitations imposed by the wave-particle duality on the simultaneous measurement of certain observables