title: Interfacial Structures of Trihexyltetradecylphosphonium-bis(mandelato)borate Ionic Liquid Confined between Gold Electrodes.
abstract: Atomistic molecular dynamics simulations have been performed to study microscopic the interfacial ionic structures, molecular arrangements, and orientational preferences of trihexyltetradecylphosphonium-bis(mandelato)borate ([P6,6,6,14][BMB]) ionic liquid confined between neutral and charged gold electrodes. It was found that both [P6,6,6,14] cations and [BMB] anions are coabsorbed onto neutral electrodes at different temperatures. The hexyl and tetradecyl chains in [P6,6,6,14] cations lie preferentially flat on neutral electrodes. The oxalato and phenyl rings in [BMB] anions are characterized by alternative parallel-perpendicular orientations in the mixed innermost ionic layer adjacent to neutral electrodes. An increase in temperature has a marginal effect on the interfacial ionic structures and molecular orientations of [P6,6,6,14][BMB] ionic species in a confined environment. Electrifying gold electrodes leads to peculiar changes in the interfacial ionic structures and molecular orientational arrangements of [P6,6,6,14] cations and [BMB] anions in negatively and positively charged gold electrodes, respectively. As surface charge density increases (but lower than 20 μC/cm2), the layer thickness of the mixed innermost interfacial layer gradually increases due to a consecutive accumulation of [P6,6,6,14] cations and [BMB] anions at negatively and positively charged electrodes, respectively, before the formation of distinct cationic and anionic innermost layers. Meanwhile, the molecular orientations of two oxalato rings in the same [BMB] anions change gradually from a parallel-perpendicular feature to being partially characterized by a tilted arrangement at an angle of 45° from the electrodes and finally to a dominant parallel coordination pattern along positively charged electrodes. Distinctive interfacial distribution patterns are also observed accordingly for phenyl rings that are directly connected to neighboring oxalato rings in [BMB] anions.
authors.affiliation: Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University , SE-106 91 Stockholm, Sweden.
authors.forename: Yong-Lei
authors.initials: YL
authors.lastname: Wang
authors.affiliation: Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University , SE-106 91 Stockholm, Sweden.
authors.forename: Mikhail
authors.initials: M
authors.lastname: Golets
authors.affiliation: Theoretical Chemistry, Chemical Center, Lund University , P.O. Box 124, SE-221 00 Lund, Sweden.
authors.forename: Bin
authors.initials: B
authors.lastname: Li
authors.affiliation: Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University , SE-106 91 Stockholm, Sweden.
authors.forename: Sten
authors.initials: S
authors.lastname: Sarman
authors.affiliation: Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University , SE-106 91 Stockholm, Sweden.
authors.forename: Aatto
authors.initials: A
authors.lastname: Laaksonen
keywords: atomistic simulations; gold electrodes; interfacial structures; molecular arrangements; trihexyltetradecylphosphonium-bis(mandelato)borate ionic liquid