What is the driving force behind the self-assembly of molecules on a surface? Why can different organizations of an assembly coexist under the same conditions? The coexistence of two experimentally observed complex phases of glutamic acid on Ag(100) is discussed using a detailed atomistic thermodynamics approach based on periodic DFT electronic energies. The interplay between bond formation and loss of degrees of freedom, corresponding to the enthalpy−entropy balance, is used to explain in detail and quantitatively the subtle equilibrium between the two differently organized self-assemblies.
Costa, D., Smerieri, M., Tranca, I., Savio, L., Vattuone, L., & Tielens, F. (2014). DFT atomistic thermodynamics applied to elucidate the driving force behind glutamic acid self-assemblies on silver (100) surface. Journal of Physical Chemistry C, 118, 29874-29879. https://doi.org/10.1021/jp509249x