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Energy fluctuations in the canonical ensemble

In the canonical ensemble, the total energy is not conserved. ( tex2html_wrap_inline468 ). What are the fluctuations in the energy? The energy fluctuations are given by the root mean square deviation of the Hamiltonian from its average tex2html_wrap_inline470 :

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Therefore

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But

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Thus,

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Therefore, the relative energy fluctuation tex2html_wrap_inline472 is given by

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Now consider what happens when the system is taken to be very large. In fact, we will define a formal limit called the thermodynamic limit, in which tex2html_wrap_inline474 and tex2html_wrap_inline476 such that N/V remains constant.

Since tex2html_wrap_inline480 and E are both extensive variables, tex2html_wrap_inline484 and tex2html_wrap_inline486 ,

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But tex2html_wrap_inline472 would be exactly 0 in the microcanonical ensemble. Thus, in the thermodynamic limit, the canonical and microcanonical ensembles are equivalent, since the energy fluctuations become vanishingly small.



Mark Tuckerman
Wed Feb 7 17:32:09 EST 2001