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Chemistry · Ch 2 — Quantum Mechanical Model of Atom

Wave particle duality of matter

2.2

Wave particle duality of matter

Albert Einstein's explanation of the photoelectric effect had already established that light shows a dual nature: it behaves as a wave in phenomena like diffraction and interference, but as a stream of particle-like photons when it exchanges energy with matter (as in the photoelectric effect). Louis de Broglie's insight, in 1924, was to turn this idea around and apply it to matter: if light - normally thought of as a wave - can behave like a particle, then perhaps particles - normally thought of as point masses - can behave like waves. He proposed that every form of matter possesses this same dual, wave-and-particle character.

Deriving the de Broglie relation. De Broglie combined two already-known expressions for the energy of a photon, one written in terms of its wave character and the other in terms of its particle character:

  • Planck's quantum hypothesis (wave character): E=hνE=h\nu\qquad — eq. (2.6)
  • Einstein's mass-energy relation (particle character): E=mc2E=mc^2\qquad — eq. (2.7)

Equating the two right-hand sides,

hν=mc2h\nu=mc^2

and using ν=c/λ\nu=c/\lambda (frequency times wavelength equals speed) gives

hcλ=mc2⇒λ=hmc— eq. (2.8)\frac{hc}{\lambda}=mc^2\qquad\Rightarrow\qquad \lambda=\frac{h}{mc}\qquad\text{— eq. (2.8)}

Equation (2.8) describes a photon, whose momentum is mcmc even though a photon has zero rest mass. For an ordinary particle of matter with mass mm travelling at velocity vv (rather than at the speed of light), the same reasoning gives the general de Broglie wavelength:

λ=hmv— eq. (2.9)\lambda=\frac{h}{mv}\qquad\text{— eq. (2.9)}

This form is valid only for particles moving much slower than light. It says that any moving particle - not just a photon - has an associated wavelength, and conversely that a wave can carry the momentum-like properties normally associated with a particle. …

Misc 2.2-worked-comparisonde Broglie wavelength of a macroscopic object versus an electron

Worked out. The textbook works two side-by-side calculations to make the significance of the de Broglie relation concrete. For a 6.626 kg iron ball moving at 10 m/s, λ=h/mv=(6.626×10−34)/(6.626×10)≈1.0×10−35\lambda=h/mv=(6.626\times10^{-34})/(6.626\times10)\approx1.0\times10^{-35} m - a length far too small ever to observe, so the ball's wave nature is completely masked. For a single electron (mass 9.11×10−319.11\times10^{-31} kg) moving at 72.73 m/s, the same formula gives λ=(6.626×10−34)/(9.11×10−31×72.73)≈1.0×10−5\lambda=(6.626\times10^{-34})/(9.11\times10^{-31}\times72.73)\approx1.0\times10^{-5} m, which is about 10510^5 angstrom - roughly a hundred thousand times the size of a single atom, and therefore large enough to produce measurable diffraction and interference effects. The comparison is the numerical proof behind the general rule stated in the text: de Broglie waves are only significant for particles of very small mass, su …