Abstract
Thermodynamics of system composed of three possible isomeric dideuteriocyclobutadienes has been studied based on the best available theoretical structural and vibrational parameters. Particular attention is paid to the recently raised question of applicability of the conventional (one term proportional to T3/2) expression for the rotational part of partition functions of the isotopomers at low temperatures T in comparison with more sophisticated approximations viz. containing an additional term proportional to T1/2 or even a correction proportional to T−1/2. Mutual relative stabilities of the isomeric isotopomers are evaluated as well as the isomerism contributions to the system thermodynamics. The three approaches are proved to yield very close results even at very low temperatures. Consequences for structure interplay in isomeric isotopomer sets are discussed.
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Slanina, Z. Rotational terms in isometric isotopomer stability evaluations: A case study of three dideuteriocyclobutadienes. Journal of Radioanalytical and Nuclear Chemistry, Articles 111, 157–164 (1987). https://doi.org/10.1007/BF02060532
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DOI: https://doi.org/10.1007/BF02060532