Finite Systems in a Heat Bath: Spectrum Perturbations and Thermodynamics

Miguel, Rodrigo de; Rubı́, J. M.

doi:10.1021/acs.jpcb.6b05591

Cited by 11 publications

(40 citation statements)

References 31 publications

(76 reference statements)

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“…In ref. 23, we show that the missing can be identified as the subdivision potential Hill introduced in his top-down nanothermodynamics 26 .…”

Section: Ifmentioning

confidence: 85%

“…refs. 23,43). Truly small systems are always embedded in some kind of environment with which they have non-trivial interactions as they evolve towards equilibrium.…”

Section: Discussionmentioning

confidence: 99%

“…In ref. 23 (eq. 43 therein) we showed that, if the solid is in its energy state, then the energy may be also be expressed as…”

Section: Ifmentioning

confidence: 99%

“…In recent work 23 we have shown that Elcock and Landberg's theory 13 of temperature-dependent energy levels provides a thermostatistical basis to the renowned Nanothermodynamics that Hill introduced in the 1960s [24][25][26] , where he proposed a new thermodynamic potential to account for non-additive interactions between small systems (for a modern review and applications of Hill's theory see refs. 27,28).…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamics Far from the Thermodynamic Limit

Miguel

Rubı́

2017

J. Phys. Chem. B

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Understanding how small systems exchange energy with a heat bath is important to describe how their unique properties can be affected by the environment. In this contribution, we apply Landsberg's theory of temperature-dependent energy levels to describe the progressive thermalization of small systems as their spectrum is perturbed by a heat bath. We propose a mechanism whereby the small system undergoes a discrete series of excitations and isentropic spectrum adjustments leading to a final state of thermal equilibrium. This produces standard thermodynamic results without invoking system size. The thermal relaxation of a single harmonic oscillator is analyzed as a model example of a system with a quantized spectrum than can be embedded in a thermal environment. A description of how the thermal environment affects the spectrum of a small system can be the first step in using environmental factors, such as temperature, as parameters in the design and operation of nanosystem properties.2

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“…In ref. 23, we show that the missing can be identified as the subdivision potential Hill introduced in his top-down nanothermodynamics 26 .…”

Section: Ifmentioning

confidence: 85%

“…refs. 23,43). Truly small systems are always embedded in some kind of environment with which they have non-trivial interactions as they evolve towards equilibrium.…”

Section: Discussionmentioning

confidence: 99%

“…In ref. 23 (eq. 43 therein) we showed that, if the solid is in its energy state, then the energy may be also be expressed as…”

Section: Ifmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Thermodynamics Far from the Thermodynamic Limit

Miguel

Rubı́

2017

J. Phys. Chem. B

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“…[20] There have been many discussions of Gibbs (Boltzmann) entropy and its relationship to thermodynamics; for examples see the references therein. [21][22][23][24][25][26][27] Here, we use a different approach.…”

Section: Relationship Between Gibbs Entropy and The Calorimetric Entropymentioning

confidence: 99%

A Derivation of the Gibbs Equation and the Determination of Change in Gibbs Entropy from Calorimetry

2016

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In this paper, we give a succinct derivation of the fundamental equation of classical equilibrium thermodynamics, namely the Gibbs equation. This derivation builds on our equilibrium relaxation theorem for systems in contact with a heat reservoir. We reinforce the comments made over a century ago, pointing out that Clausius' strict inequality for a system of interest is within Clausius' set of definitions, logically undefined. Using a specific definition of temperature that we have recently introduced and which is valid for both reversible and irreversible processes, we can define a property that we call the change in calorimetric entropy for these processes. We then demonstrate the instantaneous equivalence of the change in calorimetric entropy, which is defined using heat transfer and our definition of temperature, and the change in Gibbs entropy, which is defined in terms of the full N-particle phase space distribution function. The result shows that the change in Gibbs entropy can be expressed in terms of physical quantities.

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Nanoscale thermodynamics needs the concept of a disjoining chemical potential

Dong

2023

Nat Commun

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Disjoining pressure was discovered by Derjaguin in 1930’s, which describes the difference between the pressure of a strongly confined fluid and the corresponding one in a bulk phase. It has been revealed recently that the disjoining pressure is at the origin of distinct differential and integral surface tensions for strongly confined fluids. Here we show how the twin concept, disjoining chemical potential, arises in a reminiscent way although it comes out eighty years later. This twin concept advances our understanding of nanoscale thermodynamics. Ensemble-dependence (or environment-dependence) is one hallmark of thermodynamics of small systems. We show that integral surface tension is ensemble-dependent while differential surface tension is not. Moreover, two generalized Gibbs-Duhem equations involving integral surface tensions are derived, as well as two additional adsorption equations relating surface tensions to adsorption-induced strains. All the results obtained in this work further evidence that an approach alternative of Hill’s nanothermodynamics is possible, by extending Gibbs surface thermodynamics instead of resorting to Hill’s replica trick. Moreover, we find a compression-expansion hysteresis without any underlying phase transition.

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Finite Systems in a Heat Bath: Spectrum Perturbations and Thermodynamics

Cited by 11 publications

References 31 publications

Thermodynamics Far from the Thermodynamic Limit

Thermodynamics Far from the Thermodynamic Limit

A Derivation of the Gibbs Equation and the Determination of Change in Gibbs Entropy from Calorimetry

Nanoscale thermodynamics needs the concept of a disjoining chemical potential

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