A Legendre–Fenchel Transform for Molecular Stretching Energies
Peer reviewed, Journal article
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Original versionNanomaterials. 2020, 10 (12), 2355-2365. 10.3390/nano10122355
Single-molecular polymers can be used to analyze to what extent thermodynamics applies when the size of the system is drastically reduced. We have recently verified using molecular-dynamics simulations that isometric and isotensional stretching of a small polymer result in Helmholtz and Gibbs stretching energies, which are not related to a Legendre transform, as they are for sufficiently long polymers. This disparity has also been observed experimentally. Using molecular dynamics simulations of polyethylene-oxide, we document for the first time that the Helmholtz and Gibbs stretching energies can be related by a Legendre–Fenchel transform. This opens up a possibility to apply this transform to other systems which are small in Hill’s sense.