O(P-3) Atoms as a Chemical Probe of Surface Ordering in Ionic Liquids

TY - JOUR

T1 - O(P-3) Atoms as a Chemical Probe of Surface Ordering in Ionic Liquids

AU - Waring, Carla

AU - Bagot, Paul A. J.

AU - Slattery, John M.

AU - Costen, Matthew L.

AU - McKendrick, Kenneth G.

PY - 2010/4/15

Y1 - 2010/4/15

N2 - The reactivity of photolytically generated, gas-phase, ground-state atomic oxygen, O(P-3), with the surfaces of a series of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([NTf2]) ionic liquids has been investigated. The liquids differ only in the length of the linear CnH2n+1 alkyl side chain on the cation, with n = 2, 4, 5, 8, and 12. Laser-induced fluorescence was used to detect gas-phase OH nu' = 0 radicals formed at the gas liquid interface. The reactivity of the ionic liquids increases nonlinearly with n, in a way that cannot simply be explained by stoichiometry. We infer that the alkyl chains must be preferentially exposed at the interface to a degree that is dependent on chain length. A relatively sharp onset of surface segregation is apparent in the region of n = 4. The surface specificity of the method is confirmed through the nonthermal characteristics of both the translational and rotational distributions of the OH nu' = 0. These reveal that the dynamics are dominated by a direct, impulsive scattering mechanism at the outer layers of the liquid. The OH nu' = 0 yield is effectively independent of the bulk temperature of the longest-chain ionic liquid in the range 298-343 K, also consistent with a predominantly direct mechanism. These product attributes are broadly similar to those of the benchmark pure hydrocarbon liquid, squalane, but a more detailed analysis suggests that the interface may be microscopically smoother for the ionic liquids.

AB - The reactivity of photolytically generated, gas-phase, ground-state atomic oxygen, O(P-3), with the surfaces of a series of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([NTf2]) ionic liquids has been investigated. The liquids differ only in the length of the linear CnH2n+1 alkyl side chain on the cation, with n = 2, 4, 5, 8, and 12. Laser-induced fluorescence was used to detect gas-phase OH nu' = 0 radicals formed at the gas liquid interface. The reactivity of the ionic liquids increases nonlinearly with n, in a way that cannot simply be explained by stoichiometry. We infer that the alkyl chains must be preferentially exposed at the interface to a degree that is dependent on chain length. A relatively sharp onset of surface segregation is apparent in the region of n = 4. The surface specificity of the method is confirmed through the nonthermal characteristics of both the translational and rotational distributions of the OH nu' = 0. These reveal that the dynamics are dominated by a direct, impulsive scattering mechanism at the outer layers of the liquid. The OH nu' = 0 yield is effectively independent of the bulk temperature of the longest-chain ionic liquid in the range 298-343 K, also consistent with a predominantly direct mechanism. These product attributes are broadly similar to those of the benchmark pure hydrocarbon liquid, squalane, but a more detailed analysis suggests that the interface may be microscopically smoother for the ionic liquids.

KW - RAY PHOTOELECTRON-SPECTROSCOPY

KW - SELF-ASSEMBLED MONOLAYERS

KW - GENERATION VIBRATIONAL SPECTROSCOPY

KW - INELASTIC-SCATTERING DYNAMICS

KW - HYPERTHERMAL OXYGEN-ATOMS

KW - MOLECULAR-DYNAMICS

KW - HYDROCARBON SURFACE

KW - ENERGY-TRANSFER

KW - SQUALANE SURFACE

KW - INTERFACE

UR - http://www.scopus.com/inward/record.url?scp=77950635994&partnerID=8YFLogxK

U2 - 10.1021/jp912045j

DO - 10.1021/jp912045j

M3 - Article

SN - 1089-5639

VL - 114

SP - 4896

EP - 4904

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 14

ER -