E.S.R. and D.S.C. investigations of phase transitions in polymorphic 4-n-alkoxybenzylidene-4′-n-alkylanilines

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Abstract
It is shown that the McMillan parameter M = T SAN/T N1 (where T SAN and T NI are respectively the temperatures of the smectic A to nematic (SAN) and the nematic to isotropic (NI) phase transitions) is useful in analysing the crossover between second and first order behaviour of the SNN transition in the nO.m homologous liquid crystal series (the 4-n-alkoxybenzylidene-4′-n-alkylanilines). Using a phase diagram of orientational ordering versus M for this series, as obtained in this work (from E.S.R. and D.S.C), a symmetric tricritical point with mean field exponent β2 = 1 is demonstrated. In a preliminary study of E.S.R. linewidth parameters B and C of nitroxide spin probes dissolved in members of the nO.m series exhibiting a first order SAN transition, critical-type divergences are observed near this transition. In the case where M is closer to 0.959 (the value at the tricritical point), these divergences appear similar to those previously observed in related nO.m members with a second order SAN transition; however, they are considerably enhanced for an M value closer to unity (i.e. more removed from the tricritical point). This indicates the importance of coupling between orientational and positional order parameters in the observed critical-type divergences.