Abstract
n-Octanol and related ether alcohols are studied via molecular dynamics (MD) simulations using the two classical all-atom force fields OPLS-AA and CHARMM. The ether alcohols studied possess one ether functionality separated by varying n carbon atoms from the hydroxy group to elucidate how the positioning of the ether functionality affects intra- and intermolecular hydrogen bonding and, in turn, the physical properties of the studied alcohols. Important general trends observed from simulations with both force fields include the following: Intramolecular hydrogen bonding is majorly present in 3-butoxypropanol and 4-propoxybutanol (n = 3 and 4) while being only marginally present for 5-ethoxypentanol and 6-methoxyhexanol (n = 5 and 6) and absent in 1-hexyloxymethanol and 2-pentyloxyethanol (n = 1 and 2). The intramolecular hydrogen bonds formed by 3-butoxypropanol and 4-propoxybutanol are among the most stable ones of all present hydrogen bonds. Intermolecular hydrogen bonding is stronger between hydroxy groups (OH-OH) than between hydroxy and ether groups (OH-OE). An increased temperature causes a reduction in intermolecular OH-OH and OH-OE hydrogen bonding but a slight increase in intramolecular hydrogen bonding. A reduction in end-to-end distances at a higher temperature is also observed for all studied alcohols, which is likely a reflection of increased dihedral bond rotations. Hydrogen bonding extends mostly between just two molecules while hydrogen bonding networks are rare but do exist, involving, in some instances, up to 30 hydrogen bonds. Regardless of force field and temperature, the obtained radial distribution functions (RDFs) mostly show the same features at same distances that only vary in their intensity. 1-hexyloxymethanol forms a very specific and stable intermolecular double OH-OE hydrogen-bonded dimer. Similar double-hydrogen-bonded dimers can be found for the ether alcohols but are only significantly present for 2-pentyloxyethanol. Overall, the main difference between OPLS-AA and CHARMM is their quantitative prediction of the present hydrogen bonding speciation largely due to the stiffer dihedral potentials in OPLS-AA compared to the CHARMM force field. The simulations indicate that (a) the variations in densities are correlated to the reduced packing efficiency caused by intramolecular hydrogen bonding, (b) self-diffusion correlates with the stability of the intermolecular hydrogen bonds, and (c) the presence of hydrogen-bonded networks, although small in numbers, affect the viscosity.