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From first principles, the author gathers a few general rules that need to beabided by in the calculation of the internal partition functions (IPFs) ofindividual molecules. These rules are violated in many schemes in theliterature where occupational probabilities are used including those using thePlanck-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 whenusing occupational probabilities. Sample calculations are performed showingquantitative significance of inaccuracies caused by dishonoring such rules.

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