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A maximum entropy thermodynamics of small systems
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10.1063/1.4804549
/content/aip/journal/jcp/138/18/10.1063/1.4804549
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/18/10.1063/1.4804549
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

The distribution (β) of the temperature of the harmonic oscillator solute. As λ → ∞, (β), the distribution of β, approaches a Dirac delta distribution. Notice that at small values of λ, the (β) distribution is very broad. Hence, while ζ/λ is equivalent to the temperature of the solute, λ captures the strength of the interactions between the solvent and the solute.

Image of FIG. 2.
FIG. 2.

The experimentally observed () distribution (black circles) compared with the best-fit canonical ensemble distribution (black line, Eq. (19) ) and the best-fit of Eq. (21) (red line). Left panel shows the harmonic oscillator interacting with water molecules and the right panel shows the oscillator interacting with Lennard-Jones particles. Note that these two solvent systems have very different chemical identities. Yet, Eq. (21) describes the experimentally observed distribution over 5 orders of magnitude especially in the extended tail that the canonical ensemble distribution Eq. (19) fails to capture.

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/content/aip/journal/jcp/138/18/10.1063/1.4804549
2013-05-14
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A maximum entropy thermodynamics of small systems
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/18/10.1063/1.4804549
10.1063/1.4804549
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