Ionic-liquid (IL) mixtures hold great promise, as they allow liquids with a wide range of properties to be formed by mixing two common components rather than synthesizing large array pure ILs different chemical structures. In addition, these can exhibit and structural organization that depend on their composition, which opens up new possibilities for the composition-dependent control IL particular applications. However, fundamental properties, structure, dynamics are currently poorly...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSuperthermal widths of the collision energy distributions in hot atom reactionsWim J. Van der Zande, Rong Zhang, Richard N. Zare, Kenneth G. McKendrick, and James ValentiniCite this: Phys. Chem. 1991, 95, 21, 8205–8207Publication Date (Print):October 1, 1991Publication History Published online1 May 2002Published inissue 1 October 1991https://pubs.acs.org/doi/10.1021/j100174a035https://doi.org/10.1021/j100174a035research-articleACS...

(1989). Principles and Applications of Photochemistry. Journal Modern Optics: Vol. 36, No. 9, pp. 1276-1276.

The inelastic scattering of gas-phase OH radicals from a liquid hydrocarbon and perfluorinated polyether (PFPE) has been investigated. surfaces examined were the potentially reactive, branched squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane) inert PFPE Krytox 1506 (F−[CF(CF3)CF2O]14ave−CF2CF3). Superthermal was formed by 355-nm laser photolysis low pressure HONO above surface. Laser-induced fluorescence (LIF) used to determine relative yields nascent translational rotational...

Laser photolysis of NO2 has been combined with laser-induced fluorescence detection the nascent OH product to investigate dynamics reactions O(3P) a series saturated hydrocarbons. We confirm previous observations very low fractions rotational energy release for higher homologues such as isobutane and cyclohexane. By photolysing at shorter wavelengths produce translationally hotter atoms, we have able extend measurements previously unstudied parent members series, methane ethane. Similar...

We report an experimental investigation of the reaction O(3P)+HCl(v=2,J)→OH(v′=0 and 1,N′)+Cl(2P), where HCl is prepared in a single rovibronic level using tunable optical parametric oscillator levels OH product are monitored laser-induced fluorescence. The nascent rotational state distributions OH(v′=0 1) have been measured as function initial J HCl(v=2). These substantially rotationally excited exhibit shift towards higher N′ increased. Comparable branching into OH(v′=0) OH(v′=1) observed....

Collisions of hyperthermal oxygen atoms, with an average laboratory-frame translational energy 520 kJ mol−1, on continuously refreshed ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ([emim][NTf2]) and 1-dodecyl-3-methylimidazolium ([C12mim][NTf2]), were studied the use a beam-surface scattering technique. Time-of-flight angular distributions inelastically scattered O reactively OH H2O collected for various angles incidence rotatable mass spectrometer detector....

The liquid–vacuum interfaces of a series room-temperature ionic liquids (RTILs) containing the 1-alkyl-3-methylimidazolium cation ([Cnmim]) were investigated by reactive-atom scattering (RAS). length alkyl chain (n = 4, 6, 8, and 12) anion type (bis(trifluoromethylsulfonyl)imide ([Tf2N]), trifluoromethanesulfonate ([OTf]), tetrafluoroborate ([BF4])) varied systematically to determine their effects on preferential occupancy surface chains. experiments employed collisions with gas-phase,...

By mixing ionic liquids (ILs), it is possible to fine-tune their bulk and interfacial structure. This alters physical properties solvation behavior a simple way prepare collection of ILs whose can be tuned optimize specific application. In this study, mixtures perfluorinated alkylated have been prepared, links between composition, properties, nanostructure investigated. These different classes vary substantially in the flexibility polarizability chains. Thus, range useful structural property...

Collisions of ground-electronic-state CN radicals with the surface a prototypical saturated-hydrocarbon liquid have been studied experimentally. A molecular beam CN(X 2 Σ + ) mean laboratory-frame kinetic energy 44...

We review the experimental and theoretical work which has been carried out on dynamics of reactions O( 3 P) with saturated hydrocarbons related systems. concentrate primarily gas phase reactions, but also cover in less detail more limited condensed interfacial reactions. Although + alkane are primary focus, dominant features their compared contrasted those unsaturated alkanes, functionalised inorganic hydrides (including silanes, germanes, H 2 S, hydrogen halides). The principal techniques...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTDynamics of the reaction atomic oxygen(3P) + hydrogen bromide: experimental investigation and theoretical modelingKenneth G. McKendrick, David J. Rakestraw, Richard N. Zare, Rong ZhangCite this: Phys. Chem. 1988, 92, 19, 5530–5540Publication Date (Print):September 1, 1988Publication History Published online1 May 2002Published inissue 1 September 1988https://pubs.acs.org/doi/10.1021/j100330a039https://doi.org/10.1021/j100330a039research-articleACS...

The depolarization of OH(X Π23/2,v=0,J=1.5–6.5,e) rotational angular momentum (RAM) in collisions with He and Ar under thermal conditions (298 K) has been studied using two-color polarization spectroscopy (PS). Orientation or alignment the OH RAM was achieved circularly linearly polarized pulsed excitation, respectively, on off-diagonal A Σ2+−X Π2(1,0) band. evolution ground-state OH(X) polarization, exclusively, probed an independent, pulse tuned to diagonal Π2(0,0) PS signal decay rate...

The reactivity of photolytically generated, gas-phase, ground-state atomic oxygen, O(3P), with the surfaces a series 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([NTf2]) ionic liquids has been investigated. differ only in length linear CnH2n+1 alkyl side chain on cation, n = 2, 4, 5, 8, and 12. Laser-induced fluorescence was used to detect gas-phase OH v′ 0 radicals formed at gas−liquid interface. increases nonlinearly n, way that cannot simply be explained by...

The inelastic scattering of OH radicals from the surfaces a sequence potentially reactive organic liquids: squalane (C(30)H(62), 2,6,10,15,19,23-hexamethyltetracosane); squalene (C(30)H(50), trans-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene); and oleic acid (C(18)H(34)O(2), cis-9-octadecanoic acid) was studied experimentally. A liquid long-chain perfluorinated polyether (PFPE, Krytox® 1506) compared as chemically inert reference. Gas-phase with an average laboratory-frame...

The gas-liquid interface remains one of the least explored, but nevertheless most practically important, environments in which molecular collisions take place. These molecular-level processes underlie many bulk phenomena fundamental and applied interest, spanning evaporation, respiration, multiphase catalysis, atmospheric chemistry. We review here research that has, during past decade or so, been unraveling mechanisms inelastic reactive at interface. Armed with knowledge such outer layers...

We have investigated the reactivity of photolytically generated ground-state, gas-phase atomic oxygen O(3P) with surfaces two related ionic liquids, 1-ethyl-3-methylimidazolium ([emim]) bis(trifluoromethyl-sulfonyl)imide ([NTf2]) and 1-dodecyl-3-methylimidazolium ([C12mim]) [NTf2]. The liquids differ only in length alkyl side-chain on cation. Laser-induced fluorescence was used to detect OH radicals formed at gas−liquid interface. considerable yield from [C12mim][NTf2] comparison...

The dynamics of oxygen-atom scattering from the surfaces a series room-temperature ionic liquids containing 1-alkyl-3-methylimidazolium cation [Cnmim] and tetrafluoroborate anion [BF4] were studied by reactive-atom with mass spectrometric detection products (RAS-MS). length alkyl chain was varied (n = 4, 8, 12) in order to investigate relationship between density chains on surface their ordering. RAS-MS uses beam-surface technique hyperthermal O atom beam source rotatable spectrometer...

We describe an experimental approach to the determination of nascent internal state distribution gas-phase products a gas–liquid interfacial reaction. The system chosen for study is O(3P) atoms with surface liquid deuterated squalane, partially branched long-chain saturated hydrocarbon, C30D62. OD are detected by laser-induced fluorescence. Both (v′=0) and (v′=1) were observed in significant yield. rotational distributions both vibrational levels essentially same, characteristic Boltzmann at...

OH/OD product state distributions arising from the reaction of gas-phase O(3P) atoms at surface liquid hydrocarbon squalane C30H62/C30D62 have been measured. The were generated by 355 nm laser photolysis NO2 a low pressure above continually refreshed liquid. It has shown unambiguously that hydroxyl radicals detected laser-induced fluorescence originate surface. rotational populations are found to be partially sensitive temperature, but do not adapt it completely. In addition, temperatures...

We report the first measurements of internal energy distributions OH produced via a direct mechanism, isolated from other components on basis time-of-flight, in interfacial reaction between gas-phase O((3)P) atoms and liquid hydrocarbon squalane, C(30)H(62). were generated by laser photolysis NO(2) above liquid. Resulting hydroxyl radicals that escape surface detected laser-induced fluorescence. Time-of-flight profiles demonstrate kinetic fastest (nu' = 1) is lower than 0). Rotational...

A comparative study of the reaction family, Ca and Sr with rovibrationally selected HF or DF, has been carried out under single-collision conditions. thermal beam alkaline earth atoms, Sr, is fired into a low-pressure gas DF in which reagent molecules have prepared vibration–rotation state by use tunable infrared light source (optical parametric oscillator). The resulting monofluoride products, CaF SrF, are detected quantum-state-specific manner visible (dye laser) using laser induced...

Molecular dynamics simulations of liquid squalane, C30H62, were performed, focusing in particular on the liquid−vacuum interface. These theoretical studies aimed at identifying potentially reactive sites surface, knowledge which is important for a number inelastic and scattering experiments. A united atom force field (Martin, M. G.; Siepmann, J. I. Phys. Chem. B 1999, 103, 4508−4517) was used, analyzed with respect to their interfacial properties. modest but clearly identifiable preference...

One-colour polarization spectroscopy (PS) on the OH A 2Σ+ − X 2Π(0,0) band has been used to measure removal of bulk rotational angular momentum alignment ground-state OH(X 2Π) in collisions with He and Ar. Pseudo-first-order PS signal decays at different collider partial pressures were determine second-order decay rate constants for 2Π3/2, J = 1.5–6.5, e states. The constant, kPS, is sensitive all processes that remove population destroy polarization. contribution kPS from pure (elastic)...