On the microscopic structure of neat linear alkylamine liquids: an x-ray scattering and computer simulation study

TL;DR

This study combines x-ray scattering and molecular dynamics simulations to analyze the microscopic structure of linear alkylamine liquids, revealing weak hydrogen bonding and structural similarities to water due to charge order and molecular symmetry.

Contribution

It provides a detailed comparison of force field models in reproducing scattering features and elucidates the structural origin of the weak pre-peak in alkylamine liquids.

Findings

The pre-peak in alkylamines is much weaker than in alkanols.

The OPLS-UA model reproduces the pre-peak, unlike GROMOS-UA and CHARMM-AA.

Hydrogen-bonded clusters are confirmed, linked to charge order and molecular symmetry.

Abstract

Ambient condition linear amines, from propylamine up to nonylamine, are studied by x-ray scattering and Molecular Dynamics simulations of various force field models. The major finding is that the pre-peak in alkylamines is of about one order of magnitude weaker than that in alkanols, hence suggesting much weaker hydrogen bonding induced clustering of the amine groups than for the hydroxyl groups. Computer simulation studies reveal that OPLS-UA model reproduces the pre-peak, but with larger amplitudes, while the GROMOS-UA and CHARMM-AA force fields show almost no pre-peak. Simulations of all models reveal the existence of hydrogen bonded clusters, equally confirmed through the prominent pre-peak of the structure factor between the nitrogen atoms. But, this pre-peak gets nearly cancelled by the various combinations of the atom-atom structure factors contributions to the scattering intensity, except for the OPLS model. The purpose of this work is to understand the weakness of the scattering pre-peak from the pair correlation function perspective, considered as an order parameter associated to the concept of charge order. The difference between models is equally analyzed from the same perspective. The analysis reveals the strong charge order induced structural similarity between amines and water, as opposed to mono-ols. This is traced back to the C2v symmetry of both the water molecule and the amine head group. It explains both the existence of H-bonded clusters and the weak scattering pre-peak. Concerning the models, the presence or absence of partial charges in the methyl groups of the alkyl tails explains the presence or absence of the pre-peak in the calculated scattering intensities