Site and bond-specific dynamics of reactions at the gas-liquid interface.

The dynamics of the interfacial reactions of O((3)P) with the hydrocarbon liquids squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane) and squalene (C30H50, trans-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene) have been studied experimentally. Laser-induced fluorescence (LIF) was used to detect the nascent gas-phase OH products. The O((3)P) atoms are acutely sensitive to the chemical differences of the squalane and squalene surfaces.

Inelastic scattering of OH radicals from organic liquids: isolating the thermal desorption channel.

Inelastic scattering of OH radicals from liquid surfaces has been investigated experimentally. An initially translationally and rotationally hot distribution of OH was generated by 193 nm photolysis of allyl alcohol. These radicals were scattered from an inert reference liquid, perfluorinated polyether (PFPE), and from the potentially reactive hydrocarbon liquids squalane (C30H62, 2,6,10,15,19,23-hexamethyltetracosane) and squalene (C30H50, trans-2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene).

Dynamics of the gas-liquid interfacial reaction of O(1D) with a liquid hydrocarbon.

The dynamics of the gas-liquid interfacial reaction of the first electronically excited state of the oxygen atom, O((1)D), with the surface of a liquid hydrocarbon, squalane (C(30)H(62); 2,6,10,15,19,23-hexamethyltetracosane) has been studied experimentally. Translationally hot O((1)D) atoms were generated by 193 nm photolysis of a low pressure (nominally 1 mTorr) of N(2)O a short distance (mean = 6 mm) above a continually refreshed liquid squalane surface. Nascent OH (X(2)Π, v' = 0) reaction products were detected by laser-induced fluorescence (LIF) on the OH A(2)Σ(+)-X(2)Π (1,0) band at the same distance above the surface.

Collision dynamics and reactive uptake of OH radicals at liquid surfaces of atmospheric interest.

The inelastic scattering of OH radicals from the surfaces of a sequence of 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) was compared as a chemically inert reference. Gas-phase OH with an average laboratory-frame kinetic energy of 54 kJ mol(-1) was generated by 355-nm photolysis of a low-pressure of HONO a short distance (9 mm) above the liquid surface.