2017-16

Stochastic Molecular Thermodynamics of Small Systems: Ideal Gases

Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org

doi: 10.13140/RG.2.2.18514.45765

Abstract

Fluctuations are negligible in macroscopic systems composed of a large number of molecules;

thus, they can be described by deterministic models. The behavior of small systems (less than a
million molecules), on the other hand, requires considering such fluctuations. Although there
are different thermodynamic formulations for small systems, an alternative molecular
stochastic approach is presented, taking into account the fluctuations in molecular speeds
given by the Maxwell-Boltzmann distribution. The equations obtained are consistent with the
thermodynamics of macroscopic systems when the number of molecules considered is large.
Application examples for ideal gases include nano-sized vacuum transistors and nanobubbles.

Keywords
Entropy, Fluctuations, Ideal gas, Local temperature, Nanobubbles, Nanoscale vacuum field-
effect transistor, Small systems, Standard Maxwell-Boltzmann distribution, Thermodynamics.

1. Introduction

Thermodynamics has classically been devoted to the study of the behavior of energy (and
related properties) of macroscopic systems.[1] Statistical thermodynamics successfully
demonstrated that macroscopic properties are the result of molecular properties when
systems are extremely large.[2] More recently, stochastic thermodynamics provided a
framework for describing the behavior of small systems (e.g. colloidal systems), even out of
equilibrium.[3-6] Although thermodynamics can be regarded as a mature science, there is
clearly still some room available for improvement, in particular when trying to understand
systems below the thermodynamic size limit, or systems that have not yet reached the
thermodynamic equilibrium. The purpose of the present report is to show a molecular
stochastic approach to the thermodynamics of small systems, and particularly, of ideal gases.
This approach is consistent with the classical and statistical thermodynamics of macroscopic
systems.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

2. Volume and Energy of the System

Let us consider an arbitrary system composed of ideal gas molecules, contained in a certain
volume . In the present analysis, for simplicity, the system will be considered to be closed (no
exchange of molecules between the system and its surroundings) and non-reacting, and
therefore, the number of molecules will be constant. In general, it will be assumed that there
are different molecular species in the system, such that:

(2.1)
where , the number of molecules of species , will also be constant.

If the system considered is enclosed by a rigid boundary, then its volume will be constant. If
the boundaries of the system are flexible, then its volume might fluctuate, and it is represented
by . Unless otherwise stated, the more general variable volume will be considered.

The diacritical tilde mark ( ) represents, in this work, a random variable. The expected value
of a random variable is denoted by the diacritical straight bar ( ), and the variance is ,
where the symbol of the corresponding random variable is included in the subscript. A symbol
without any diacritics represents either a deterministic variable or a constant value. Molar
properties are represented by manuscript letters.

The fluctuating molar volume ( ) of the system is defined as the total volume of the system
divided by the number of moles of substance:

(2.2)
where is Avogadros constant.

Given that there is a linear relationship between the molar volume and the system volume (for
a closed, non-reacting system), the expected value and variance of the molar volume are
simply:
( ) ()

(2.3)

( ) ( ) () ( )
(2.4)

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Another relevant definition related to the volume of the system is the molecular number
density:

(2.5)
which is a random variable with expected value:

( ) ( ) ( )

(2.6)

Please notice that for a random variable , ( )
, unless .

Furthermore, the variance of the number density is:

( )

(2.7)

The results obtained in Eq. (2.6) and (2.7) show significant differences when dealing with
nonlinear functions of random variables instead of deterministic variables.

On the other hand, the total internal energy of the system ( ) will then be the sum of the total
internal kinetic energy ( ) and the total internal potential energy ( ). Assuming that the
molecules behave as ideal gases, then the total internal potential energy approaches zero, as
the net molecular interaction potential acting on each molecule is considered negligible. Even
though interaction potentials are neglected, molecular collisions are not.

Thus, for an ideal gas, the total energy of the system will be the result of summing the kinetic
energy of each molecule in the system:

(2.8)

Now, considering the molecules as small hard spheres (neglecting any internal motion), the
kinetic energy of each molecule will be given only by its translational motion. Thus,

(2.9)
Eq. (2.9) is the basis of the present molecular stochastic thermodynamics approach.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

3. Temperature and the Maxwell-Boltzmann distribution

In a previous report, it was shown that as a result of multiple molecular collisions, molecular
speeds become randomly distributed following the generalized Maxwell-Boltzmann
distribution:[7]

( )

(3.1)

where represents a particular realization of the random molecular speed , is the mass of
species , is Boltzmanns constant, and is the mean (expected)
system temperature.

It was also shown, that any molecular speed can be expressed in terms of the standard
Maxwell-Boltzmann random variable ( ) as:[8]

(3.2)

where is the average molecular speed of species in the system, and represents a random
number following the standard Maxwell-Boltzmann distribution, such that ( ) and
( ) .

Thus, the total internal energy of the system can be expressed as:

(3.3)

where the subscript in indicates that each molecule has a different random value from the
exact same standard Maxwell-Boltzmann distribution.

In previous reports, the standard Maxwell-Boltzmann random variable was denoted by , without any
diacritics; however, for notation consistency along this work, the diacritical tilde mark is used .

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Eq. (3.3) allows describing the internal energy of any system as a function only of the average
temperature and the standard Maxwell-Boltzmann random variables; that is, the internal
energy is also a random variable.

The average, expected value of the internal energy of the system will then be:

( ) ( ) ( )

(3.4)

which is a very well-known expression for the macroscopic total internal energy of an ideal
gas.[2] Please also notice that ( ) .[9]

Furthermore, the variance of the total internal energy is:

( ) ( ) ( ) ( )

(3.5)

given the fact that ( ) .[9]

The coefficient of variation for the internal energy then becomes:

( )

(3.6)

This result indicates that for macroscopic systems , the coefficient of variation for the
internal energy approaches zero, meaning that the internal energy practically behaves as a
deterministic variable. For systems below the macroscopic thermodynamic limit, such energy
fluctuations cannot be neglected. For example, if the system is composed of
molecules, its relative fluctuation will be , which can be considered significant.

On the other hand, it was previously mentioned that is the mean temperature of the system.
In fact, the actual system temperature can also be considered as a random variable defined
as:[10]

(3.7)
with the following properties:

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

( )
(3.8)

(3.9)

( )

(3.10)

Furthermore, from Eq. (3.3) and (3.7) it can be concluded that:

(3.11)

which is similar to the classical expression, but now and represent random variables.

The corresponding molar internal energy ( ) is:

(3.12)
with
( )

(3.13)

( )

(3.14)

( )

(3.15)

4. Pressure, Virial and Enthalpy

If we consider a system contained in a rigid vessel (with a very high elastic modulus), then, as
long as the pressure difference between both sides of the vessel is small (compared to the
yield strength of the material), the volume inside the vessel can be considered to be constant.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

For stainless steel, for example, the yield strength is about Pa,[11] which is almost
times larger than ambient pressure.

The pressure that molecules of an ideal gas at mean temperature and contained in a
constant volume exerts on the walls of the container (internal pressure) can be determined
using the virial equation for ideal gases:[12]

(4.1)

where is the gas constant, and , the molecular number density,

is now constant too.

The expected value, variance and coefficient of variation for the pressure of this system are:

( )

(4.2)

( )
(4.3)

( )

(4.4)

Eq. (4.1) corresponds to the very well-known equation of state for ideal gases.[1]

If, on the other hand, the container is elastic then the volume of the system will be variable. In
that case, both internal ( ) and external ( ) pressures are practically the same, and
therefore the virial equation becomes:

(4.5)

Since the external pressure is independent of the internal temperature of the system, Eq. (4.5)
can be better expressed as:

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

(4.6)

Thus,

( ) ( )

(4.7)

() [ ( ) ( ) ( ) ]


[ ( ( ) ) ( ) ]

[( )( ( ) ) ( ) ]

(4.8)

( )( ( ) ) ( )
()
( )
(4.9)

If the external pressure can be considered as constant ( ), Eq. (4.6) to (4.9)

becomes:

(4.10)

()

(4.11)

( )

(4.12)

()

(4.13)

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of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

In general, the virial equation can be expressed as a function of the fluctuating wall virial ( )
as:

(4.14)
where
()
(4.15)

(4.16)

()

(4.17)
Now, given that the total enthalpy ( ) of a system is defined as:[1]

(4.18)
Then, using Eq. (3.3) and (4.14) in Eq. (4.18):

(4.19)
with:
( )

(4.20)

( )

(4.21)

( )

(4.22)
Thus, for an ideal gas the following relationships hold true:

(4.23)

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

The molar enthalpy ( ) of the system is:

(4.24)
with
( )

(4.25)

( )

(4.26)

( )

(4.27)

5. Thermodynamic coefficients

Let us now calculate some relevant thermodynamic coefficients for an ideal gas.

The molar constant-volume heat capacity of a substance is defined as:[1]

( )
( ) ( )

(5.1)
On the other hand, the molar constant-pressure heat capacity is:

( )
( ) ( )

(5.2)

Thus, it can be seen that the molar heat capacities of an ideal gas system are constant.

Now, the ratio between the constant-pressure and the constant-volume molar heat capacities
is:

(5.3)

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

On the other hand, the difference between the constant-pressure and the constant-volume
molar heat capacities is:

(5.4)

Another important coefficient is the volume expansivity of the system (at constant pressure
corresponding to the external pressure ), which is defined as:[1]

( )
( ) ( )

(5.5)

Please notice that the volume expansivity is a random variable with an expected value of:

( ) ( )

(5.6)
given that (
) , for ,[9] and its variance is:

( ) ( ) ( )

(5.7)
since (
) , for .[9]

It is also important to remark that:

(5.8)
which means that , and .

Similarly, the isothermal compressibility is defined as:[1]

( )
( ) ( )


(5.9)

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of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

The expected value and variance of the isothermal compressibility will depend on the particular
probability distribution of the external pressure. If the external pressure is constant, the
isothermal compressibility will also be constant.

Finally, let us consider the Joule-Thompson coefficient defined as:[1]

( ) ( )

(5.10)
Thus, from Eq. (4.23) and (5.2):
( )
( )

(5.11)
That is, for ideal gases (even in small systems), the enthalpy is independent of the pressure.

6. Entropy

Clausius defined the concept of entropy as:[13]

(6.1)

Please notice that even though is the differential of a random variable , the differential
itself behaves as a deterministic variable.[14]

Eq. (6.1) can be expressed in terms of the internal energy as:

(6.2)
Using the definitions given in Eq. (5.1) and (4.5), results in:

( )

(6.3)

Integrating Eq. (6.3) from an initial reference state { } to a final state { } yields:

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

( ) ( )

(6.4)
Using the definition presented in Eq. (4.6):

( ) ( ) ( ) ( )

(6.5)
Now, from Eq. (3.7):


( ) ( )

[ ( ) ( ) ( )] ( )

(6.6)

For systems with a moderate number of molecules (larger than 20), then:[9]

[ ( ) ( ( )) ( ( ))] ( )

[ ( ) ( ) ( )] ( )

(6.7)

where represents a standard normal random variable with ( ) and ( ) .

Expanding in series the logarithms involving the standard random variables results in:

[ ( ) ( ) ( )] ( )

(6.8)

Assuming that the external pressure also behaves as a random variable, with constant
expected value and constant variance , then Eq. (6.8) becomes:

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

[ ( ) ( ) ( )]

[ ( ) ( )]

(6.9)

Truncating the series in Eq. (6.9) after the second term, results in:

( )
[ ( ) ( ) ]

[ ( ) ( ) ( )]

(6.10)

The expected value of the entropy change is therefore:

( ) ( )

(6.11)
and its variance is:

( ) [ ( ) ( ) ]

(6.12)

If the external pressure is almost constant ( ), then

(6.13)
and

( )

( ) ( )

(6.14)
The molar entropy of the system will be:

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

[ ( ) ( ) ( )] ( )

(6.15)

with

( ) ( )

(6.16)
and for a constant external pressure:

( )
(6.17)

( )

( )

(6.18)
If the volume of the system remains constant, Eq. (6.3) results in:

[ ( ) ( ) ( )]

(6.19)
with

( ) ( )

(6.20)
( )
(6.21)

And the corresponding molar entropy change (for constant volume) becomes:

[ ( ) ( ) ( )]

(6.22)
with

( ) ( )

(6.23)

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 Stochastic Molecular Thermodynamics
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Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

( )
(6.24)

( )

( )

(6.25)

7. Helmholtz and Gibbs Free Energies

The total Helmholtz free energy is defined as:[1]

(7.1)
The change in Helmholtz free energy between two different states of the system is:[14]

(7.2)
with (using Eq. 3.4 and 6.11, and considering a constant external pressure):

( ) ( ) ( )

(7.3)
The corresponding molar Helmholtz free energy change is:

(7.4)
with:

( ) ( )

(7.5)
On the other hand, the total Gibbs free energy of the system is defined as:[1]

(7.6)
where the change between two states is:

( )

(7.7)

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

with (for constant external pressure):

( ) ( ) ( )

(7.8)
The corresponding expressions for the molar Gibbs free energy are:

(7.9)
with:

( ) ( ) ( )

(7.10)

The corresponding expressions of the molar free energy change for constant volume are:

( ) ( )

(7.11)

( ) ( ) ( )

(7.12)

8. Application Examples

8.1 Nanoscale vacuum field-effect transistor.

Vacuum tubes were one of the basic key components of early electronics, including radios,
televisions and computers, until they were replaced by smaller, cheaper integrated circuits. In
an attempt to get the advantages of electron ballistic transport provided by vacuum
technologies with the small size and low cost of solid state technologies, vacuum
microelectronics and later, vacuum nanoelectronics (devices with dimensions in the order of
nanometers) have been developed.[15] Given that a true vacuum is not possible, vacuum
nanoelectronic devices provide channels smaller than the electron mean free path in air in
order to reduce undesirable collisions. These vacuum nanolectronic transistors are promising
devices, which could potentially further reduce size and cost, and increase capacity of
electronics components.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Let us consider a vacuum field-effect transistor with a rectangular channel of , and an

area of , operating at 0.1 Pa and ambient temperature ( ).[16] The volume of
the channel is . Because the transistor operates under vacuum, air remaining
inside the channel can be considered to behave ideally.[17] From Eq. (4.2), the expected
number of air molecules in the channel is:

(8.1)

The gas temperature inside the channel will fluctuate with a standard deviation of (Eq. 3.9):

(8.2)
and the pressure in the channel, with a standard deviation (from Eq. 4.4):

(8.3)

The molar internal energy of the gas inside the channel has an average value of
(Eq. 3.13) with a standard deviation of (Eq. 3.15). And the molar enthalpy of the
gas in the channel has a mean value of (Eq. 4.25) and standard deviation of
(Eq. 4.27).

Assuming that the mean ambient temperature remains constant, the average change in molar
entropy for constant volume is zero (Eq. 6.20), but the standard deviation of the molar entropy
change is (from Eq. 6.24):

(8.4)

The behavior of the gas inside the channel was simulated using Monte Carlo (MC)
simulation,[18] considering that the speed of the molecules in the channel changes randomly
following the corresponding Maxwell-Boltzmann distribution (Eq. 3.1). The interaction between
gas molecules is neglected (assuming ideal gas behavior). For simplicity, it is assumed that the
gas is pure Nitrogen. The Monte Carlo algorithm was programmed in R (https://cran.r-
project.org/), and the simulation was performed with molecules in a simulation cell of
. Figure 1 and Figure 2 show the results obtained in local temperature
and entropy change, respectively, after different runs of the MC simulation algorithm.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Figure 1. Local temperature inside the channel of a vacuum field-effect transistor operating at
0.1 Pa and ambient temperature, for 10000 MC simulation runs. The number of N2 molecules in
the channel is 608.

Figure 2. Molar entropy change inside the channel of a vacuum field-effect transistor operating
at 0.1 Pa and ambient temperature, for 10000 MC simulation runs. The number of N 2 molecules
in the channel is 608.

The average local temperature obtained from the MC simulation was , with a standard
deviation of . On the other hand, the average molar entropy change obtained from the
simulation was , with a standard deviation of . Both results are in
agreement with the theoretical calculations (Eq. 8.2 and 8.4, respectively).

The algorithm code in R for the corresponding MC simulation can be found in the Appendix.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

8.2 Ozone nanobubble.

Nanobubbles are spherical gas bubbles whose diameter is less than . Although it was
initially predicted that bubbles at the nanoscale will have a brief lifetime (less than );
recent experimental results demonstrated that nanobubbles are surprisingly stable, not only
when adsorbed on a surface, but also in bulk.[19] Nanobubbles have quickly gained scientific
and industrial interest in applications such as water treatment, biomedical engineering, water
disinfection, surface cleaning, degradation of organic pollutants, and many others.[20] In
particular, the use of ozone nanobubbles in water is a promising antimicrobial agent for the
treatment and prevention of several infectious diseases.[21,22] The size of ozone nanobubbles
can range typically from to .

Thus, as an example of application of stochastic molecular thermodynamics, let us consider the

thermodynamic behavior of a single spherical ozone nanobubble containing ozone
molecules, present in a bath of water at ambient conditions, located at different positions in
the bath.

Let us consider that the bath of water has a mean total level of . Thus, the pressure
( ) at a certain height from the bottom of the bath will be:

( )
(8.5)

where represents the atmospheric pressure, is the mass density of water, and
is the standard gravity. Neglecting the fluctuations in ambient pressure, water
density and total level of water in the bath, results in:

(8.6)

If the ambient temperature is , then the fluctuation in local temperature of the gas in
the nanobubble will be given by (from Eq. 3.9):

(8.7)

The volume of the nanobubble containing ozone molecules, will depend on its position
. Thus, from Eq. (4.10) and (8.6):

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

(8.8)

If the atmospheric pressure is , and the mass density of water is , then:

(8.9)

(8.10)
For a perfectly spherical bubble, the diameter ( ) of the bubble is:

(8.11)

The expected value of the diameter ( ) and its standard deviation ( ) should be obtained by
solving the following set of algebraic equations**:

( )
(8.12)

( )
(8.13)

This leads to a relative fluctuation in nanobubble diameter given by:

( )

(8.14)

Figure 3 shows the effect of position on the average diameter and its standard deviation for
nanobubbles with ozone molecules, where it can be observed an expansion of the
nanobubble (at constant number of molecules) as it approaches the surface of the bath.

**
The set of nonlinear algebraic equations can be solved by any suitable numerical method, e.g. the
substitution method.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Figure 3. Effect of vertical position of a nanobubble with 10000 ozone molecules in a water
bath on its average diameter and standard deviation.

Now, according to Eq. (6.15), the difference in molar entropy between the top and the bottom
of the bath (with constant average temperature, independent of position) is:

[ ( ) ( )] ( )

(8.15)
with expected value:
( )

(8.16)
and standard deviation:

(8.17)

Figure 4. Effect of vertical position of a nanobubble with 10000 ozone molecules in a water
bath on its expected molar entropy change from the bottom of the bath.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Thus, if the nanobubble rises, its molar entropy increases. This, of course, does not take into
account interactions with the medium. Figure 4 shows the expected change in molar entropy
from the bottom of the bath to any arbitrary position .

9. Conclusion

The present stochastic molecular thermodynamics formulation for ideal gases, based on the
description of the fluctuation in molecular speeds in a system, allows describing the behavior
of small systems (less than a million molecules). This approach is consistent with classical
macroscopic thermodynamics in the limit when the number of molecules in the system is large.
Even though the description of expected values of thermodynamic properties is very similar to
the classical thermodynamics formulation, the stochastic molecular thermodynamics approach
allows describing the fluctuation of thermodynamic variables in terms of the fluctuation in
molecular speeds, following the generalized Maxwell-Boltzmann distribution. It was also
shown that the predictions of the model are consistent with Monte Carlo simulations, in an
example involving nano-sized vacuum transistors. In a second example, the size distribution of
nanobubbles comprising 10000 ozone molecules each, as a function of their position in a bath
was obtained. Further improvements in the model are possible, including the description of
non-ideal gases and condensed phases, and a more detailed description of the interactions at
the walls/interfaces.

Acknowledgments

The author gratefully acknowledges Prof. Jaime Aguirre (Universidad Nacional de Colombia)
for valuable discussions and reviewing the manuscript; and Prof. Dr. Farid Chejne (Universidad
Nacional de Colombia) also for helpful discussions.

This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.

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[2] Kaznessis, Y. N. (2011). Statistical Thermodynamics and Stochastic Kinetics: An Introduction

for Engineers. Cambridge University Press.

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of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

[3] Van den Broeck, C. (2013). Stochastic thermodynamics: a brief introduction. In: Bechinger,
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155-193.

[4] Esposito, M. (2012). Stochastic thermodynamics under coarse graining. Physical Review E,
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[5] Seifert, U. (2012). Stochastic thermodynamics, fluctuation theorems and molecular

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[6] Seifert, U. (2008). Stochastic thermodynamics: principles and perspectives. The European
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[7] Hernandez, H. (2017). On the generalized validity of the Maxwell-Boltzmann distribution and
the zeroth Law of Thermodynamics. ForsChem Research Reports 2017-4. doi:
10.13140/RG.2.2.26937.16480.

[8] Hernandez, H. (2017). Standard Maxwell-Boltzmann distribution: Definition and properties.

ForsChem Research Reports 2017-2. doi: 10.13140/RG.2.2.29888.74244.

[9] Hernandez, H. (2017). Standard Maxwell-Boltzmann Distribution: Additional Nonlinear and

Multivariate Properties. ForsChem Research Reports 2017-14. doi: 10.13140/RG.2.2.35761.07520.

[10] Hernandez, H. (2017). Analysis of Temperature fluctuations in ideal gases - From the
macroscopic to the molecular scale. ForsChem Research Reports 2017-3. doi:
10.13140/RG.2.2.19208.83203.

[11] Askeland, D. R., Fulay, P. P., & Wright, W. J. (2011). The science and engineering of materials.
6th Ed. Stamford: Cengage Learning.

[12] Clausius, R. (1870). XVI. On a mechanical theorem applicable to heat. The London,
Edinburgh, and Dublin Philosophical Magazine and Journal of Science, 40(265), 122-127.

[13] Clausius, R. (1854), Ueber eine vernderte Form des zweiten Hauptsatzes der
mechanischen Wrmetheorie. Ann. Phys., 169: 481506. doi: 10.1002/andp.18541691202.

[14] Hernandez, H. & Aguirre, J. (2017). Calculus of Random Finite Differences and Differentials.
ForsChem Research Reports 2017-15. doi: 10.13140/RG.2.2.31562.67529.

[15] Stoner, B. R., & Glass, J. T. (2012). Nanoelectronics: Nothing is like a vacuum. Nature
Nanotechnology, 7(8), 485-487.

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

[16] Wang, X., Shen, Z., Wu, S., & Zhang, J. (2017). Vacuum field-effect transistor with a deep
submicron channel fabricated by electro-forming. Solid-State Electronics, 132, 1-5.

[17] Hernandez, H. (2017). Clausius molecular sphere of action in crowded systems: Non-ideal
gas behavior. ForsChem Research Reports 2017-11. doi: 10.13140/RG.2.2.36384.07681.

[18] Ferguson, D. M., Siepmann, J. I. & Truhlar, D. G. (1999). Monte Carlo methods in chemical
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Langmuir, 32(43), 11086-11100.

[20] Agarwal, A., Ng, W. J., & Liu, Y. (2011). Principle and applications of microbubble and
nanobubble technology for water treatment. Chemosphere, 84(9), 1175-1180.

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Periodontal Disease. ARC Journal of Dental Science, 1(3), 1-2.

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rehabilitation. U.S. Patent No. 7,488,416. Washington, DC: U.S. Patent and Trademark Office.

Appendix. Monte Carlo Simulation algorithm in R for the gas inside the channel
of a nanoscale vacuum field-effect transistor.

#Monte Carlo simulation of the gas in a nanoscale VFET channel

#Hugo Hernandez
#ForsChem Research
#08/12/2017

#Standard Maxwell-Boltzmann random numbers generator

randMB<-function(n){
B=abs(-0.3033*log((((runif(n)+0.005)^(-0.4))-0.9974)/7.326))
return(B)
}

#Random unit direction generator

rugen<-function(n){
u=1-2*runif(3*n)
u=matrix(u,nrow=n, ncol=3)
u=u/sqrt(rowSums(u^2))
return(u)
}

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

#Main script
#Constants
kB=1.3806e-23 #J/K
Na=6.022e23 #mol^-1
R=kB*Na #J/molK
Da=1.66e-27 #kg

#Size of the rectangular channel

L=c(0.25,2.5,5) #um
V=8e-18*L[1]*L[2]*L[3] #m^3

#Simulation conditions
N=806 #Number of molecules in the channel
m=28*Da #Molecular mass (Nitrogen)
d=3.1e-10 #Molecular diameter (m)
Tm=298.15 #K
Pm=0.1 #Pa
niter=10000 #Number of iterations

#Initialization of variables
x=array(0,dim=c(N,3)) #Positions
v=array(0,dim=c(N,3)) #Velocities
Ur={} #Molar internal energy record
Hr={} #Molar enthalpy record
Tr={} #Local temperature record
Pr={} #Pressure record
dSr={} #Molar entropy change record
dAr={} #Molar Helmholtz free energy change record
dGr={} #Molar Gibbs free energy change record

#Initial molecular positions and velocities

x[,1]=t((1-2*runif(N))*L[1]) #Initial position
x[,2]=t((1-2*runif(N))*L[2]) #Initial position
x[,3]=t((1-2*runif(N))*L[3]) #Initial position
vm=sqrt(8*kB*Tm/(pi*m)) #Mean speed um/us
v0=vm*randMB(N) #Initial speeds
u0=rugen(N) #Initial velocity directions
v[,1]=v0*u0[,1] #Initial velocities
v[,2]=v0*u0[,2] #Initial velocities
v[,3]=v0*u0[,3] #Initial velocities
U=0.5*Na*m*sum(v*v)/N #Molar Internal energy J/mol
T=2*U/(3*R) #Local temperature K
H=5*R*T/2 #Molar enthalpy J/mol
P=N*kB*T/V #Pressure Pa
S=0 #Initial reference molar entropy J/molK
A=0 #Ref.molar Helmholtz free energy J/mol
G=0 #Reference molar Gibbs free energy J/mol

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 Stochastic Molecular Thermodynamics
of Small Systems: Ideal Gases
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

U0=U #Initial molar internal energy

H0=H #Initial molar enthalpy

i=1 #Initialization of iteration counter

#Simulation loop
while (i<=niter) {
#Data recording
Ur=c(Ur,U) #Molar internal energy record
Hr=c(Hr,H) #Molar enthalpy record
Tr=c(Tr,T) #Local temperature record
Pr=c(Pr,P) #Pressure record
dSr=c(dSr,S) #Molar entropy change record
dAr=c(dAr,A) #Molar Helmholtz free energy change record
dGr=c(dGr,G) #Molar Gibbs free energy change record

#Update positions and velocities

x[,1]=t((1-2*runif(N))*L[1]) #Initial position
x[,2]=t((1-2*runif(N))*L[2]) #Initial position
x[,3]=t((1-2*runif(N))*L[3]) #Initial position
vm=sqrt(8*kB*Tm/(pi*m)) #Mean speed um/us
v0=vm*randMB(N) #Initial speeds
u0=rugen(N) #Initial velocity directions
v[,1]=v0*u0[,1] #Initial velocities
v[,2]=v0*u0[,2] #Initial velocities
v[,3]=v0*u0[,3] #Initial velocities
Uold=U #Previous molar internal energy J/mol
Hold=H #Previous molar enthalpy J/mol
Told=T #Previous temperature K
Sold=S #Previous entropy change J/molK
U=0.5*Na*m*sum(v*v)/N #Molar Internal energy J/mol
T=2*U/(3*R) #Local temperature K
H=5*R*T/2 #Molar enthalpy J/mol
P=N*kB*T/V #Pressure Pa
dU=U-Uold #Molar internal energy change J/mol
S=(3*R/2)*log(T/Told) #Molar entropy change J/molK
A=dU-(Sold*(T-Told))-(T*S) #Molar Helmholtz free energy J/mol
G=H-Hold-(Sold*(T-Told))-(T*S) #Molar Gibbs free energy J/mol
i=i+1 #Update iteration counter
}

#Plot results
plot(Tr,xlab='Monte Carlo Simulation run',ylab='Local temperature (K)')

plot(dSr,xlab='Monte Carlo Simulation run',ylab='Molar entropy change (J/

molK)')

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