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Number of States and Probabilities

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In order to systematize the study of a system using the method of state counting, we aim to establish a direct relationship between the probability of finding the system at a particular energy and the number of associated states.

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System in contact with a heat reservoir

Equation

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Suppose a system with energy E_r is in contact with a thermal reservoir of energy E'.

A thermal reservoir is understood as a system whose temperature remains constant. One way to achieve this is by having a large reservoir (like a water bath).

If both systems are isolated from the surroundings, the sum of their energies will remain constant, which can be expressed with as

E_0=E_r+E_h

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This version provides clarity while retaining the essential information.

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Probability of finding the system in a state r

Equation

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The probability of finding the system in a state where it has an energy E_r, while the reservoir has an energy E' = E_0 - E_r, is defined as

P_r = C \cdot \Omega_r(E_r) \cdot \Omega'(E')



where C is a constant that is adjusted to ensure the probability is normalized.

Since P_r represents the probability of finding the system in a particular state r, the number of states in state r is equal to one. In other words, this implies that

\Omega_r(E_r) = 1



Therefore, the probability can be expressed with respect to as

P_r=C_h\Omega_h(E_0-E_r)

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Normalization Condition

Equation

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If we sum the probabilities of each state r, the result should be one. This signifies that it is normalized with the :

\sum_rP_r=1

This is equivalent to stating that the system must necessarily be in one of the possible states.

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Development of the number of states in Taylor series

Equation

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As the energy E_r is much smaller than the total energy E_0, the logarithm of the number of states can be expanded around the energy E_r as follows:

\ln\Omega'(E_0-E_r)=\ln\Omega'(E_0)-\left.\displaystyle\frac{\partial\Omega'}{\partial E'}\right\vert_0E_r\ldots



Since the derivative of the logarithm of the number of states is equal to the beta function:

\beta=\left.\displaystyle\frac{\partial\Omega'}{\partial E'}\right\vert_0



It follows that, in a first approximation with ,

\ln\Omega_h(E_0-E_r)=\ln\Omega_h(E_0)-\beta E_r

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Equation for the Probability of State r

Equation

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If we substitute the expression

\ln\Omega_h(E_0-E_r)=\ln\Omega_h(E_0)-\beta E_r



with beta del sistema 1/J, energía del estado r J, energía del sistema J and número de Estados -

into the equation for probability with constante de Normalización -, energía del estado r J, energía del sistema J, número de Estados - and probabilidad del estado r -,

P_r=C_h\Omega_h(E_0-E_r)

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we obtain with constante de Normalización -, energía del estado r J, energía del sistema J, número de Estados - and probabilidad del estado r - the probability

P_r=Ce^{-\beta E_r}

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where C is a constant to be determined using the normalization condition.

The expression e^{-\beta E} is referred to as the Boltzmann factor, and the distribution it describes is known as the canonical distribution.

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Normalization constant

Equation

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Under the normalization condition with estado r - and probabilidad del estado r -,

\sum_rP_r=1

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it is obtained that the normalization constant C is equal to estado r - and probabilidad del estado r -:

C^{-1}=\sum_re^{-\beta E_r}

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