Liquid Crystals (LC), anisotropic fluids that combine many tensor properties of crystalline solids with the fluidity of liquids, have long been providing major challenges to theorists and molecular modelers. In the classical textbook picture a molecule giving rise to LC phases is represented by a uniaxial rod endowed with repulsive (Onsager) or attractive (Maier-Saupe) interactions or possibly with a combination of the two (van der Waals picture) [1]. While these models have proved able to reproduce at least qualitatively the most common LC phase, the nematic one, and its phase transition to a normal isotropic fluid, they have not been able to deal with quantitative aspects (e.g. the orientational order at the transition) and more seriously, with the variety of novel LC phases and of sophisticated experiments offering increasing detailed observations at the nanoscale. Classical Monte Carlo and molecular dynamics computer simulations that have been successfully used for some time on simple lattice or off-lattice generic models [2-5] have started to offer unprecedented, atomistic level, details of the molecular organization of LC in the bulk and close to surfaces [6,7]. In particular, atomistic simulations are now starting to offer predictive power, opening the possibility of closing the gap between molecular structure and phase organizations. The availability of detailed data from these virtual experiments requires to generalize LC models inserting molecular features like deviation from uniaxiality or rigidity, the inclusion of partial charges etc. Such more detailed descriptions should reflect also in the link between molecular and continuum theories, already developed for the simplest models [8,9], possibly opening the way to a molecular identification of the material and temperature dependent coefficients in Landau-deGennes type free energy functionals.
[1] see, e.g., G. R. Luckhurst and G. W. Gray, eds., The Molecular Physics of Liquid Crystals (Academic Press,, 1979).
[2] P. Pasini and C. Zannoni, eds., Advances in the computer simulations of liquid crystals (Kluwer, 1998)
[3] O. D. Lavrentovich, P. Pasini, C. Zannoni and S. Zumer, eds. Defects in Liquid Crystals: Computer Simulations, Theory and Experiments, (Kluwer, Dordrecht , 2001).
[4] C. Zannoni, Molecular design and computer simulations of novel mesophases, J. Mat. Chem. 11, 2637 (2001).
[5] R.Berardi, L.Muccioli, S.Orlandi, M.Ricci, C.Zannoni, Computer simulations of biaxial nematics, J. Phys. Cond. Matter 20, 1 (2008).
[6] G. Tiberio, L. Muccioli, R. Berardi and C. Zannoni , Towards “in silico” liquid crystals. Realistic Transition temperatures and physical properties for n-cyanobiphenyls via molecular dynamics simulations, ChemPhysChem 10, 125 (2009).
[7] O. Roscioni, L. Muccioli, R. Della Valle, A. Pizzirusso, M. Ricci and C. Zannoni, Predicting the anchoring of liquid crystals at a solid surface: 5-cyanobiphenyl on cristobalite and glassy silica surfaces of increasing roughness, Langmuir 29, 8950 (2013).
[8] 1. J. Katriel, G. F. Kventsel, G. R. Luckhurst and T. J. Sluckin, Free-energies in the Landau and Molecular-field approaches, Liq. Cryst. 1, 337 (1986).
[9] J. M. Ball and A. Majumdar, Nematic liquid crystals: From Maier-Saupe to a Continuum Theory, Mol. Cryst. Liq. Cryst. 525, 1 (2010).