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We present a combined x-ray diffraction and infrared spectroscopy study onthe phase behavior and molecular dynamics of n-hexadecanol in its bulk stateand confined in an array of aligned nanochannels of 8 nm diameter in mesoporoussilicon. Under confinement the transition temperatures between the liquid, therotator RII and the crystalline C phase are lowered by approximately 20K. Whilebulk n-hexadecanol exhibits at low temperatures a polycrystalline mixture oforthorhombic beta- and monoclinic gamma-forms, geometrical confinement favorsthe more simple beta-form: only crystallites are formed, where the chain axisare parallel to the layer normal. However, the gamma-form, in which the chainaxis are tilted with respect to the layer normal, is entirely suppressed. Thebeta-crystallites form bi-layers, that are not randomly orientated in thepores. The molecules are arranged with their long axis perpendicular to thelong channel axis. With regard to the molecular dynamics, we were able to showthat confinement does not affect the inner-molecular dynamics of the CH_2scissor vibration and to evaluate the inter-molecular force constants in the Cphase.

Phase transitions and molecular dynamics of n-hexadecanol confined in silicon nanochannels