Fundamental View on the Calculation of Internal Partition Functions Using Occupational Probabilities

Abstract

From first principles, the author gathers a few general rules that need to be abided by in the calculation of the internal partition functions (IPFs) of individual molecules. These rules are violated in many schemes in the literature where occupational probabilities are used including those using the Planck-Larkin partition function (PLPF) within the chemical picture. Considering these rules is useful from conceptual and practical points of view. A solution is introduced to assure fulfilling the above mentioned rules when using occupational probabilities. Sample calculations are performed showing quantitative significance of inaccuracies caused by dishonoring such rules.

15 pages, 4 figures, under review

References in corpus (4)

• On the ionization equilibrium of hot hydrogen plasma and thermodynamic-consistency of formulating finite internal partition functions
• On the calculation of equilibrium thermodynamic properties and the establishment of statistical-thermodynamically-consistent finite bound-state partition functions in nonideal multi-component plasma mixtures within the chemical model
• Inconsistency in Fermi's probability of the quantum states
• Comment on "On the ionization equilibrium of hot hydrogen plasma and thermodynamic consistency of formulating finite partition functions"

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