From Nanowerk News:

Scientists have long suspected that the way materials behave on the nanoscale – that is when particles have dimensions of about 1–100 nanometres – is different from how they behave on any other scale. A new paper in the journal Chemical Science (“Solvation and surface effects on polymorph stabilities at the nanoscale”) provides concrete proof that this is the case.The laws of thermodynamics govern the behaviour of materials in the macro world, while quantum mechanics describes behaviour of particles at the other extreme, in the world of single atoms and electrons.

But in the middle, on the order of around 10–100,000 molecules, something different is going on. Because it’s such a tiny scale, the particles have a really big surface-area-to-volume ratio. This means the energetics of what goes on at the surface become very important, much as they do on the atomic scale, where quantum mechanics is often applied.Classical thermodynamics breaks down.

But because there are so many particles, and there are many interactions between them, the quantum model doesn’t quite work either.

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