Affiliation:
1. Institut für Physik, Johannes Gutenberg-Universität Mainz 1 , Staudingerweg 7-9, 55128 Mainz, Germany
2. Institute for Theoretical Physics IV, University of Stuttgart 2 , 70569 Stuttgart, Germany
Abstract
Conventional gas–liquid phase transitions feature a coexistence line that has a monotonic and positive slope in line with our intuition that cooling always leads to condensation. Here, we study the inverse phenomenon, condensation of adsorbed organic molecules into dense domains upon heating. Our considerations are motivated by recent experiments [Aeschlimann et al., Angew. Chem., Int. Ed. 60, 19117–19122 (2021)], which demonstrate the partial dissolution of an ordered molecular monolayer and the mobilization of molecules upon cooling. We introduce a simple lattice model in which each site can have three states corresponding to unoccupied and two discernible molecular conformations. We investigate this model through Monte Carlo simulations, mean-field theory, and exact results based on the analytical solution of the Ising model in two dimensions. Our results should be broadly applicable to molecules with distinct conformations that have sufficiently different entropies or heat capacities.
Funder
Deutsche Forschungsgemeinschaft
Subject
Physical and Theoretical Chemistry,General Physics and Astronomy