Quantum statistics matter when thermal energy is comparable with a characteristic vibrational level spacing. The chain's natural angular frequency is , givingFactors of order unity depend on which vibrational scale is used. The largest chain phonon angular frequency is , corresponding to . An isolated two-atom bond has reduced mass and angular frequency , corresponding to . Thus quantum corrections become appreciable on the scale of several tens of kelvin, and all modes are classical only when is comfortably above the largest relevant vibrational scale. Below it, high-frequency phonons are progressively frozen out and equipartition fails.
For the isolated bond, the zero-temperature root-mean-square relative displacement isIt is small enough for a local bond expansion. The classical weakly anharmonic estimate in part d therefore has a useful parametric windowwhere the lower condition means comfortably above the vibrational scale, rather than a sharp threshold. The model's upper bound concerns local anharmonicity and binding, not a prediction of the melting temperature.
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