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research papers
Several statistical approaches to anharmonic motion are known, but there exists no comparison between different formalisms. Therefore the most common formalisms (potential, Edgeworth and Gram-Charlier expansions and α formalism) are compared with each other in part I of this series of papers. Mathematical shortcomings of the potential and Edgeworth expansions may lead to doubtful interpretations of the corresponding probability densities and the potentials. The a formalism works inefficiently in conventional crystallographic refinement programs; it tends to converge badly and its computation is very time consuming. The best results of all are obtained for the Gram-Charlier expansion, which can be easily expanded to tensors up to sixth rank.