How Does the Most Probable Energy Minimize Helmholtz Free Energy?

In summary, the conversation discusses the relationship between the most probable energy and the Helmholtz free energy. The Helmholtz free energy can be expressed as F=E-TS(E), where S(E) is the entropy of the system with energy E. The probability P(E) of the system having energy E is given by P(E) = 1/Z *weight function*exp(-beta E), where beta is the inverse of temperature and Z is the partition function. Taking the logarithm of P(E) leads to the desired result of F=E-TS(E), as the probability is maximal when the logarithm is maximal. The post mentioned in the conversation provides a detailed explanation of how free energy is minimized using a specific example
  • #1
captainjack2000
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Homework Statement


Show that the most probable energy minimises the Helmholtz free energy.


Homework Equations


F=E-TS(E) where S(E) is the entropy of te system of given energy E.

The Attempt at a Solution


Not sure how you would 'show' is ?

P(E) = 1/Z *weight funciton*exp(-beta E)
 
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  • #2
The probablity that a system at temperature T is in a state r with energy E_r is given by exp[-E_r/(k T)]/Z

The probability that the system has an energy between
E and E + dE is thus the probability that the system is in any particular state with eneergy E times the number of states inside the energy range from E to E + dE. The probability density P(E) as a function of energy is thus:

P(E) = Omega(E)/(delta E) exp[-E/(k T)]/Z

where delta E is the energy resolution used to define Omega(E). If you take the logarithm, use that S = k Log(Omega), then you find the desired result.
 
  • #3
I'm sorry but I am really not following what you said. Why would you take the logarithm of the probability? and how does this relate to the free energy F=E-TS(E)?
 
  • #4
captainjack2000 said:
I'm sorry but I am really not following what you said. Why would you take the logarithm of the probability? and how does this relate to the free energy F=E-TS(E)?

If you take the log then E - TS pops out. And that's the free energy.
 
  • #5
The probability is maximal if the logarithm of the probability is maximal and vice versa. If you take the logarithm then you see that:

Log[P(E)]= -F(E) + constant

where the constant does not depend on E.
 

FAQ: How Does the Most Probable Energy Minimize Helmholtz Free Energy?

What is the concept of minimizing Helmholtz free energy?

Helmholtz free energy, also known as Helmholtz energy or A energy, is a thermodynamic potential that describes the amount of work that can be extracted from a thermodynamic system at constant temperature and volume. Minimizing Helmholtz free energy is the process of finding the lowest possible value of this potential, which corresponds to the most stable state of the system.

Why is it important to minimize Helmholtz free energy?

Minimizing Helmholtz free energy is important because it allows us to predict the equilibrium state of a system. In nature, systems tend to evolve towards states of minimum energy, so by minimizing Helmholtz free energy, we can determine the most stable state of a system and understand how it will behave under different conditions.

How is Helmholtz free energy related to entropy?

Helmholtz free energy is closely related to entropy, which is a measure of the disorder or randomness of a system. The lower the Helmholtz free energy of a system, the lower its entropy will be. In other words, minimizing Helmholtz free energy results in a more ordered and stable system.

What factors affect the Helmholtz free energy of a system?

The Helmholtz free energy of a system is affected by its temperature, pressure, and composition. It also depends on external factors such as the presence of an electric or magnetic field. Changes in any of these factors can alter the Helmholtz free energy of a system and affect its stability.

How is Helmholtz free energy calculated?

Helmholtz free energy is calculated using the equation A = U - TS, where A is the Helmholtz free energy, U is the internal energy of the system, T is the temperature, and S is the entropy. However, this equation is only valid for systems at constant temperature and volume. For more complex systems, other equations and techniques may be used to calculate Helmholtz free energy.

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