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PHYS7322 Problem Set 5: Thermodynamics

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5 views3 pages

PHYS7322 Problem Set 5: Thermodynamics

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abdullahmutahar27
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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PHYS7322 - Nonequilibrium Physics - Fall 2024

Problem set 5
Due date TBA

1. Class notes exercise 1. Derive the thermodynamic relation


 
∂G
H =G−T
∂T p

where H = E + pV is the enthalpy and G = E + pV − T S is the Gibbs


free-energy.
2. Class notes exercise 2. Derive the equilibrium relation

hH 2 i − hHi2 = kT 2 cp

for the variance of the the enthalpy during spontaneous fluctuations in ther-
modynamic equilibrium where cp = (∂H/∂T )p is the specific heat at constant
pressure. Hint: use thermodynamic relation derived in exercise 1 together
with the expression for the Gibbs free-energy

G = −kT ln Y

where ∞
ΠN 3 3
Z Z
dV i=1 d pi d qi −(E+pV )/kT
Y = e
0 V0 h3N N !
is the partition function in the (N, p, T ) ensemble. Note that the volume
factor V0 is only introduced here to make Y dimensionless but does not
affect thermodynamic quantities obtained from derivatives of G with respect
to the intensive variables T and P .
3. Class notes exercise 3. The continuity relation for the heat Q, which is a
statement of energy conservation, is given by
~ · ~jQ = 0
∂t Q + ∇

where
~ + cp ~q(~r, t)
~jQ = −κ∇T
is the total heat current and q(~r, t) is the fluctuating part of this current,
which is uncorrelated in space and time

hqj (~r, t)ql (~r, t0 )i = FT δjl δ(~r − ~r0 )δ(t − t0 ).

Use the result of exercise 2 to determine the constant FT using the same
steps as for the analysis of the concentration fluctuations in the class notes.
Then, by following the same steps as for the diffusion constant in the class
notes, validate the Green-Kubo relation for the thermal conductivity by a
direct calculation Z ∞
1
κ= h~jQ
T
(0) · ~jQ
T
(t)idt
3V kT 2 0
where Z
~jQ
T
(t) = dV ~jQ
T
(~r, t)
V

is the total heat current inside a volume V . f

4. Class notes exercise 4. The Green-Kubo relation for the thermal conduc-
tivity can be implemented in molecular dynamics simulations by defining the
total heat current as
~jQ
T d X
(t) = ~ri i
dt i
where
m 2 1X
i = |~vi | + U (|~ri − ~rj |)
2 2 j

is the energy of particle i, which is the sum of its kinetic energy and poten-
tial energy assuming for simplicity pairwise interactions with all the other
particles through a potential U (|~ri − ~rj |) that only depends on the distance
between particles. Derive the relation
X 1 XX  
~jQ
T
(t) = ~vi i + (~ri − ~rj ) F~ij · ~vi
i
2 i j6=i

where F~ij is the force exerted on particle i by particle j.

5. Onsager reciprocity relations and chemical reactions


Consider the chemical reaction where a molecular susbtance can exist in
three states A, B, and C, and transform from state β to state α at a rate
kαβ following the scheme depicted schematically in (3.1) of Onsager’s paper
Physical Review 37, 405-426 (1931).

(a) Write down an expression for the equilibrium free-energy F (nA , nB , nc )


of a system of N = n molecules in terms of the numbers nA , nB , and nC
of molecules in each state, which satisfy the constraint nA + nB + nC =
n, and the partition functions ZA , ZB , and ZC , of single molecules in
states A, B, and C, respectively. Recall that the partition function
Z = ZAnA ZBnB ZCnC /(nA !nB !nC !) and F = −kT log Z.
(b) Derive expressions for the equilibrium values of nA , nB , and nC , denoted
by n̄A , n̄B , and n̄C by minimizing F under the constraint that nA +nB +
nC = n. A simple way to implement this constraint is to substitute
nC = n − nA − nB and minimize F with respect to nA and nB . This
yields two equation that together with the constraint nA + nB + nC = n
uniquely determine the equilibrium values of nA , nB , and nC .
(c) Show that for small fluctuations from equilibrium, i.e. (nα −n̄α )/n̄α  1,
the free-energy can be written in the form
X (nα − n̄α )2
F (nA , nB , nc ) ' Fmin + kT
α=A,B,C
2̄nα

where Fmin = F (n̄A , n̄B , n̄c ).


(d) The thermodynamic driving forces conjugate to nα are

∂F
Xα = − for α = A, B, C.
∂nα
The reaction kinetics, which drives the system towards thermodynamic
equilibrium, can be expressed in terms of those forces in the form

d(nα − n̄α ) X
= Lαβ Xβ
dt β=A,B,C

where Lαβ is a 3 × 3 matrix of coefficients. By comparing the above set


of kinetic equations to those obtained from the mass action law, show
that the detailed balance condition

kαβ n̄β = kβα n̄α

imposes the reciprocal relation

Lαβ = Lβα

for all off-diagonal elements of the matrix (i.e. elements with α 6= β).

Common questions

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Representing free-energy in this quadratic form emphasizes the stability of the system around its equilibrium state. It reflects that deviations from equilibrium are minimized and energetically penalized in proportion to their square, suggesting a harmonic approximation akin to Hooke's law. This representation highlights how minor fluctuations revert towards the stable equilibrium, ensuring that such systems naturally tend to their lowest energy configuration over time, thus quantifying the system's response to fluctuations .

The pairwise potential interaction defines the interaction energy between particles, which is necessary to calculate the total heat current. Specifically, for molecular dynamics simulations, the total heat current jTQ(t) encompasses both kinetic and potential contributions where the potential interaction energy U(|ri - rj|) affects how energy is shared among particles, and contributes via terms such as Σi Σj≠i (ri - rj) (Fij · vi) to the total heat current, reflecting the microstate interactions and energy exchanges .

The fluctuating heat current q(r, t) is considered uncorrelated in space and time because it simplifies the statistical mechanics calculations and reflects the random nature of microscopic processes. This assumption is fundamental in deriving the Green-Kubo relation since it allows the mathematical treatment of fluctuations to demonstrate their contribution to macroscopic thermal conductivity, ultimately validating κ = 1/(3V kT^2) ∫ ⟨jTQ(0) · jTQ(t)⟩ dt .

The expression G = -kT ln Y allows analysis of macroscopic thermodynamic quantities because Y is the partition function encompassing all microstates' contributions to the system's state. By taking derivatives of G with respect to intensive properties like temperature and pressure, one can derive other macroscopic properties like enthalpy and specific heat. This facilitates the transition from microstate summation in Y to macroscopic behavior captured by G .

Implementing the Green-Kubo relations in molecular dynamics simulations involves challenges such as accurately calculating the time-correlation functions for fluctuating currents over numerous time intervals, ensuring statistical convergence due to fluctuating interaction energies, and dealing with the immense computational effort required for tracking particle interactions and energy exchanges over time while maintaining the precision of microscopic details .

The derivation begins with the definition of enthalpy, H = E + pV, and Gibbs free energy, G = E + pV - TS. By differentiating the expression for Gibbs free energy with respect to temperature at constant pressure and substituting into the enthalpy definition, the connection between these two quantities is illustrated as H = G − T(∂G/∂T)p .

The expressions for the equilibrium values are derived by minimizing the free energy F = -kT log Z under the constraint nA + nB + nC = N, where Z is the partition function. By substituting nC = N - nA - nB and using the Lagrange multiplier method, the derivatives of F with respect to nA and nB are set to zero, yielding two equations. These, in combination with nA + nB + nC = N, provide the system of equations to solve for the equilibrium values of nA, nB, and nC .

The detailed balance condition, kαβnβ = kβαnα, ensures that at equilibrium, the forward and backward reaction rates are equal, which is a prerequisite for the system to maintain equilibrium. This condition imposes the reciprocity relation Lαβ = Lβα for the kinetic coefficients in the linear response framework, illustrating that each pairwise interaction between states (α, β) exhibits symmetry, thus satisfying the Onsager reciprocity relations necessary for the description of irreversible processes in thermodynamic systems .

The expression for Z indicates that the probability distribution across microstates contributes significantly to the properties of the system, such as entropy and free-energy. The presence of factorial terms accounts for the indistinguishability of particles and enforces combinatorial symmetry, which affects entropy calculations. Additionally, the multiplicative nature of the partition functions (ZnA A ZB ZnC C) shows how contributions from individual states aggregate, reflecting overall thermodynamic behavior derived from state-specific contributions .

The variance relation ⟨H2⟩−⟨H⟩2 = kT2cp shows the link between the fluctuation of enthalpy in a thermodynamic system and its specific heat at constant pressure. This relation is significant because it provides insight into how microscopic fluctuations manifest in measurable macroscopic quantities, such as cp, and reflects the energy distribution within the system .

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