On the X-ray Scattering Pre-peak of Linear Mono-ols and the Related Microstructure from Computer Simulations

The X-ray scattering intensities (I(k)) of linear alkanols OH(CH₂)CH₃ obtained from experiments (methanol to 1-undecanol) and computer simulations (methanol to 1-nonanol) of different force field models are comparatively studied particularly in order to explain the origin and the properties of the scattering pre-peak in the k-vector range 0.3-1 Å^-1. The experimental I(k) values show two apparent features: the pre-peak position k_P decreases with increasing n, and more intriguingly, the amplitude A_P goes through a maximum at 1-butanol (n = 4). The first feature is well reproduced by all force-field models, while the second shows strong model dependence. The simulations reveal various shapes of clusters of the hydroxyl head-group from n>2. k_P is directly related to the size of the meta-objects corresponding to such clusters surrounded by their alkyl tails. The explanation of the A_P turnover at n = 4 is more involved in terms of cancellations of atom-atom structure factor S(k) contributions related to domain ordering. The flexibility of the alkyl tails tends to reduce the cross contributions, thus revealing the crucial importance of this parameter in the models. Force fields with all-atom representation are less successful in reproducing the pre-peak features for smaller alkanols, n<6, possibly because they blur the charge ordering process since all atoms bear partial charges. The analysis clearly shows that it is not possible to obtain a model-free explanation of the features of I(k).