Inside out Approach to Rotator State in Hydrogen-Bonded System—Experimental and Theoretical Cross-Examination in n-Octanol

The experimental and theoretical description of premelting behavior is one of the most challenging tasks in contemporary material science. In this paper, n-octanol was studied using a multi-method approach to investigate it at macroscopic and molecular levels. The experimental infrared (IR) spectra were collected in the solid state and liquid phase at temperature range from [Formula: see text] [Formula: see text] C to −15 [Formula: see text] C to detect temperature-related indicators of pretransitional phenomena. Next, the nonlinear dielectric effect (NDE) was measured at various temperatures (from −30 [Formula: see text] C to −15 [Formula: see text] C) to provide insight into macroscopic effects of premelting. As a result, a two-step mechanism of premelting in n-octanol was established based on experimental data. It was postulated that it consists of a rotator state formation followed by the surface premelting. In order to shed light onto molecular-level processes, classical molecular dynamics (MD) was performed to investigate the time evolution of the changes in metric parameters as a function of simulation temperature. The applied protocol enabled simulations in the solid state as well as in the liquid (the collapse of the ordered crystal structure). The exact molecular motions contributing to the rotator state formation were obtained, revealing an enabling of the rotational freedom of the terminal parts of the chains. The Car–Parrinello molecular dynamics (CPMD) was applied to support and interpret experimental spectroscopic findings. The vibrational properties of the stretching of OH within the intermolecular hydrogen bond were studied using Fourier transformation of the autocorrelation function of both dipole moments and atomic velocity. Finally, path integral molecular dynamics (PIMD) was carried out to analyze the quantum effect’s influence on the bridged proton position in the hydrogen bridge. On the basis of the combined experimental and theoretical conclusions, a novel mechanism of the bridged protons dynamics has been postulated—the interlamellar hydrogen bonding pattern, resulting in an additional OH stretching band, visible in the solid-state experimental IR spectra.