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Systematic microcanonical inflection-point analysis of precise numerical results obtained in extensive generalized-ensemble Monte Carlo simulations reveals a bifurcation of the coil-globule transition line for polymers with a bending stiffness exceeding a threshold value. The region, enclosed by the toroidal and random-coil phases, is dominated by structures crossing over from hairpins to loops upon lowering the energy. Conventional canonical statistical analysis is not sufficiently sensitive to allow for the identification of these separate phases.

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