Probing the interfacial structure of aqueous surfactants through helium atom evaporation.

Dissolved helium atoms evaporate from liquids in super-Maxwellian speed distributions because their interactions are too weak to enforce full thermal equilibration at the surface as they are "squeezed" out of solution. The excess speeds of these He atoms reflect their final interactions with solvent and solute molecules at the surfaces of water and other liquids. We extend this observation by monitoring He atom evaporation from salty water solutions coated with surfactants. These surface-active molecules span neutral, anionic, and cationic amphiphiles: butanol, 3-methyl-1-butanol, pentanol, pentanoic acid, pentanoate, tetrabutylammonium, benzyltrimethylammonium, hexyltrimethylammonium, and dodecyltrimethylammonium, each characterized by surface tension measurements. The helium energy distributions, recorded in vacuum using a salty water microjet, reveal a sharp distinction between neutral and ionic surfactant films. Helium atoms evaporate through neutral surfactant monolayers in speed distributions that are similar to a pure hydrocarbon, reflecting the common alkyl chains of both. In contrast, He atoms appear to evaporate through ionic surfactant layers in distributions that are closer to pure salty water. We speculate that the ionic surfactants distribute themselves more loosely and deeply through the top layers of the aqueous solution than do neutral surfactants, with gaps between the surfactants that may be filled with salty water. This difference is supported by prior molecular dynamics simulations and ion scattering measurements of surfactant solutions.

Creation and Reaction of Solvated Electrons at and near the Surface of Water.

Solvated electrons (es-) are among nature's most powerful reactants, with over 2600 reactions investigated in bulk water. These electrons can also be created at and near the surface of water by exposing an aqueous microjet in vacuum to gas-phase sodium atoms, which ionize into es- and Na+ within the top few layers. When a reactive surfactant is added to the jet, the surfactant and es- become coreactants localized in the interfacial region. We report the reaction of es- with the surfactant benzyltrimethylammonium in a 6.7 M LiBr/water microjet at 235 K and pH = 2. The reaction intermediates trimethylamine (TMA) and benzyl radical are identified by mass spectrometry after they evaporate from solution into the gas phase. Their detection demonstrates that TMA can escape before it is protonated and benzyl before it combines with itself or a H atom. Diffusion-reaction calculations indicate that es- reacts on average within 20 Å of the surface and perhaps within the surfactant monolayer itself, while unprotonated TMA evaporates from the top 40 Å. The escape depth exceeds 1300 Å for the more slowly reacting benzyl radical. These proof-of-principle experiments establish an approach for exploring the near-interfacial analogues of aqueous bulk-phase radical chemistry through the evaporation of reaction intermediates into the gas phase.

Solvent-Mediated Charge Transfer Dynamics of a Model Brown Carbon Aerosol Chromophore: Photophysics of 1-Phenylpyrrole Induced by Water Solvation.

Nitrogen heterocycles are known to be important light-absorbing chromophores in a newly discovered class of aerosols, commonly referred to as "brown carbon" (BrC) aerosols. Due to their significant absorption and spectral overlap with the solar actinic flux, these BrC chromophores steer the physical and optical properties of aerosols. To model the local aqueous solvation environment surrounding BrC chromophores, we generated cold molecular complexes with water and a prototypical BrC chromophore, 1-phenylpyrrole (1PhPy), using supersonic jet-cooling and explored their intermolecular interactions using single-conformation spectroscopy. Herein, we utilized resonant two-photon ionization (R2PI) and UV holeburning (UV HB) double-resonance spectroscopies to obtain a molecular-level understanding of the role of water microsolvation in charge transfer upon photoexcitation of 1PhPy. Quantum chemical calculations and one-dimensional discrete variable representation simulations revealed insights into the charge transfer efficacy of 1PhPy with and without addition of a single water molecule. Taken together, our results indicate that the intermolecular interactions with water guide the geometry of 1PhPy to adopt a more twisted intramolecular charge transfer (TICT) configuration, thus facilitating charge transfer from the pyrrole donor to the phenyl ring acceptor. Furthermore, the water network surrounding 1PhPy reports on the charge transfer such that the H2O solvent primarily interacts with the pyrrole ring donor in the ground state, whereas it preferentially interacts with the phenyl ring acceptor in the excited state. Large Franck-Condon activity is evident in the 1PhPy + 1H2O excitation spectrum for the water-migration vibronic bands, supporting H2O solvent reorganization upon excitation of the 1PhPy chromophore. Fluorescence measurements with increasing H2O % volume corroborated our gas-phase studies by indicating that a polar water solvation environment stabilizes the TICT configuration of 1PhPy in the excited electronic state, from which emission is observed at a lower energy compared to the locally excited configuration.

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A2Σ+) with H2, N2, and CO: Intermolecular Interactions Drive Collision Outcomes.

Intermolecular interactions, stereodynamics, and coupled potential energy surfaces (PESs) all play a significant role in determining the outcomes of molecular collisions. A detailed knowledge of such processes is often essential for a proper interpretation of spectroscopic observations. For example, nitric oxide (NO), an important radical in combustion and atmospheric chemistry, is commonly quantified using laser-induced fluorescence on the A2Σ+ ← X2Π transition band. However, the electronic quenching of NO (A2Σ+) with other molecular species provides alternative nonradiative pathways that compete with fluorescence. While the cross sections and rate constants of NO (A2Σ+) electronic quenching have been experimentally measured for a number of important molecular collision partners, the underlying photochemical mechanisms responsible for the electronic quenching are not well understood. In this paper, we describe the development of high-quality PESs that provide new physical insights into the intermolecular interactions and conical intersections that facilitate the branching between the electronic quenching and scattering of NO (A2Σ+) with H2, N2, and CO. The PESs are calculated at the EOM-EA-CCSD/d-aug-cc-pVTZ//EOM-EA-CCSD/aug-cc-pVDZ level of theory, an approach that ensures a balanced treatment of the valence and Rydberg electronic states and an accurate description of the open-shell character of NO. Our PESs show that H2 is incapable of electronically quenching NO (A2Σ+) at low collision energies; instead, the two molecules will likely undergo scattering. The PESs of NO (A2Σ+) with N2 and CO are highly anisotropic and demonstrate evidence of electron transfer from NO (A2Σ+) into the lowest unoccupied molecular orbital of the collision partner, that is, the harpoon mechanism. In the case of ON + CO, the PES becomes strongly attractive at longer intermolecular distances and funnels population to a conical intersection between NO (A2Σ+) + CO and NO (X2Π) + CO. In contrast, for ON + N2, the conical intersection is preceded by an ∼0.40 eV barrier. Overall, our work shines new light into the impact of coupled PESs on the nonadiabatic dynamics of open-shell systems.

Dynamical signatures from competing, nonadiabatic fragmentation pathways of S-nitrosothiophenol.

S-Nitrosothiols (RSNOs) are derived from the combination of sulfur and nitric oxide (NO) radicals in the Earth's atmosphere and fragment to products following photolysis. Extensive theoretical studies have focused on the thermodynamic and, to a lesser extent, photochemical properties of RSNOs. However, experimental studies of these compounds have been limited due to the inherent instability of RSNOs at room temperature. Using velocity map imaging (VMI), we explore the photodissociation dynamics of jet-cooled S-nitrosothiophenol (PhSNO) from 355 nm photolysis. We report the translational and internal energy distributions of the NO and thiophenoxy (PhS) co-fragments, which are determined by spatial detection of the ionized NO photofragments using 1+1 resonance-enhanced multiphoton ionization (REMPI). The velocity distributions indicate competing PhSNO nonadiabatic dissociation pathways, in which PhS is formed in the ground and first excited electronic states when probing high- and low-energy NO (X2Π1/2, v'', J'') rovibrational states, respectively. The results of multireference electronic structure calculations suggest that direct dissociation on the bright S2 state results in PhS formed in its excited electronic state, whereas intersystem crossing into the triplet manifold leads to population of PhS in its electronic ground state. The dynamical signatures from the dissociation processes are imprinted on the fragments' quantum states and relative translation, which we explore in rigorous detail using state-resolved imaging and high-level theoretical calculations.

Imaging the nonreactive collisional quenching dynamics of NO (A2Σ+) radicals with O2 (X3Σg -).

Nitric oxide (NO) radicals are ubiquitous chemical intermediates present in the atmosphere and in combustion processes, where laser-induced fluorescence is extensively used on the NO (A2Σ+ ← X2Π) band to report on fuel-burning properties. However, accurate fluorescence quantum yields and NO concentration measurements are impeded by electronic quenching of NO (A2Σ+) to NO (X2Π) with colliding atomic and molecular species. To improve predictive combustion models and develop a molecular-level understanding of NO (A2Σ+) quenching, we report the velocity map ion images and product state distributions of NO (X2Π, v″ = 0, J″, Fn, Λ) following nonreactive collisional quenching of NO (A2Σ+) with molecular oxygen, O2 (X3Σg -). A novel dual-flow pulse valve nozzle is constructed and implemented to carry out the NO (A2Σ+) electronic quenching studies and to limit NO2 formation. The isotropic ion images reveal that the NO-O2 system evolves through a long-lived NO3 collision complex prior to formation of products. Furthermore, the corresponding total kinetic energy release distributions support that O2 collision coproducts are formed primarily in the c1Σu - electronic state with NO (X2Π, v″ = 0, J″, Fn, Λ). The product state distributions also indicate that NO (X2Π) is generated with a propensity to occupy the Π(A″) Λ-doublet state, which is consistent with the NO π* orbital aligned perpendicular to nuclear rotation. The deviations between experimental results and statistical phase space theory simulations illustrate the key role that the conical intersection plays in the quenching dynamics to funnel population to product rovibronic levels.