Entropy-driven phases at high coverage adsorption of straight rigid rods on three-dimensional cubic lattices

PASINETTI, P. M.; RAMIREZ-PASTOR, A. J.; VOGEL, E. E.

Physical Review E

American Physical Society

Año: 2023 vol. 107

2470-0045

Combining Monte Carlo simulations and thermodynamic integration method, we study the configurational entropy per site of straight rigid rods of length k (k-mers) adsorbed on three-dimensional (3D) simple cubic lattices. The process is monitored by following the dependence of the lattice coverage θ on the chemical potential μ (adsorption isotherm). Then, we perform the integration of μ(θ ) over θ to calculate the configurational entropy per site of the adsorbed phase s(k, θ ) as a function of the coverage. Based on the behavior of the function s(k, θ ), different phase diagrams are obtained according to the k values: k 4, disordered phase; k = 5, 6, disorderedand layered-disordered phases; and k 7, disordered, nematic and layered-disordered phases. In the limit of θ → 1 (full coverage), the configurational entropy per site is determined for values of k ranging between 2 and 8. For k 6, MC data coincide (within the statistical uncertainty) with recent analytical predictions [D. Dhar and R. Rajesh, Phys. Rev. E 103, 042130 (2021)] for very large rods. This finding represents the first numerical validation of the expression obtained by Dhar and Rajesh for d-dimensional lattices with d > 2. In addition, for k 5, the values of s(k, θ → 1) for simple cubic lattices are coincident with those values reported in [P. M. Pasinetti et al., Phys. Rev. E 104, 054136 (2021)] for two-dimensional (2D) square lattices. This is consistent with the picture that at high densities and k 5, the layered-disordered phase is formed on the lattice. Under theseconditions, the system breaks to 2D layers, and the adsorbed phase becomes essentially 2D. The 2D behavior of the fully covered lattice reinforces the conjecture that the large-k behavior of entropy per site is superuniversal, and holds on d-dimensional hypercubical lattices for all d 2.