Phase transitions in the adsorbed molecular chains

Abstract

Rotational excitations of molecular adsorbed layers are studied theoretically. Nonlinear dynamical equations are obtained with accounting of quadrupolar interactions between molecules and freezing of translational degrees of freedom. The equilibrium positions of the molecules are found to be experimentally observed structures with alternating rotational ordering of planar rotors along the direction to the nearest neighbor (for linear or square structures) under low temperature. Dynamical analysis gives an integral of motion (energy) of the chain that in the long-wave limit leads consequently to the existence of four phases. The first one corresponds to oscillations near equilibrium ordered states. The second phase corresponds to low-energy rotational excitations along ‘valleys’ (easy directions in the effective potential) that do not destroy strong correlations between molecules while structural data can show rotational disorder (melting). The third phase corresponds to an energy that is enough to travel between ‘valleys’; only some ‘islands’ in the angle space are forbidden. Complete destruction of correlation when the energy is over the peaks of the effective potential corresponds to the fourth phase. Therefore rotational melting is a complex phenomenon that has several stages.