Valence Electronic Structure of Interfacial Phenol in Water Droplets.

Biochemistry and a large part of atmospheric chemistry occur in aqueous environments or at aqueous interfaces, where (photo)chemical reaction rates can be increased by up to several orders of magnitude. The key to understanding the chemistry and photoresponse of molecules in and "on" water lies in their valence electronic structure, with a sensitive probe being photoelectron spectroscopy. This work reports velocity-map photoelectron imaging of submicrometer-sized aqueous phenol droplets in the valence region after nonresonant (288 nm) and resonance-enhanced (274 nm) two-photon ionization with femtosecond ultraviolet light, complementing previous liquid microjet studies. For nonresonant photoionization, our concentration-dependent study reveals a systematic decrease in the vertical binding energy (VBE) of aqueous phenol from 8.0 ± 0.1 eV at low concentration (0.01 M) to 7.6 ± 0.1 eV at high concentration (0.8 M). We attribute this shift to a systematic lowering of the energy of the lowest cationic state with increasing concentration caused by the phenol dimer and aggregate formation at the droplet surface. Contrary to nonresonant photoionization, no significant concentration dependence of the VBE was observed for resonance-enhanced photoionization. We explain the concentration-independent VBE of ∼8.1 eV observed upon resonant ionization by ultrafast intermediate state relaxation and changes in the accessible Franck-Condon region as a consequence of the lowering of the intermediate state potential energy due to the formation of phenol excimers and excited phenol aggregates. Correcting for the influence of electron transport scattering in the droplets reduced the measured VBEs by 0.1-0.2 eV.

Direct Observation of a Roaming Intermediate and Its Dynamics.

Chemical reactions are often characterized by their transition state, which defines the critical geometry the molecule must pass through to move from reactants to products. Roaming provides an alternative picture, where in a dissociation reaction, the bond breaking is frustrated and a loosely bound intermediate is formed. Following bond breaking, the two partners are seen to roam around each other at distances of several Ångstroms, forming a loosely bound, and structurally ill-defined, intermediate that can subsequently lead to reactive or unreactive collisions. Here, we present a direct and time-resolved experimental measurement of roaming. By measuring the photoelectron spectrum of UV-excited acetaldehyde with a femtosecond extreme ultraviolet pulse, we captured spectral signatures of all of the key reactive structures, including that of the roaming intermediate. This provided a direct experimental measurement of the roaming process and allowed us to identify the time scales by which the roaming intermediate is formed and removed and the electronic potential surfaces upon which roaming proceeds.

Preparation of Tautomer-Pure Molecular Beams by Electrostatic Deflection.

Tautomers are ubiquitous throughout chemistry and typically considered inseparable in solution. Yet (bio)chemical activity is highly tautomer-specific, with common examples being the amino and nucleic acids. While tautomers exist in an equilibrium in solution, in the cold environment of a molecular beam the barrier to tautomerization is typically much too high for interconversion, and tautomers can be considered separate species. Here we demonstrate the first separation of tautomers within a molecular beam and the production of tautomerically pure gas-phase samples. We show this for the 2-pyridone/2-hydroxypyridine system, an important structural motif in both uracil and cytosine. Spatial separation of the tautomers is achieved via electrostatic deflection in strong inhomogeneous fields. We furthermore collect tautomer-resolved photoelectron spectra using femtosecond multiphoton ionization. This paves the way for studying the structure-function-dynamic relationship on the level of individual tautomers, using approaches that typically lack the resolution to do so, such as ultrafast dynamics experiments.

Single-Color Isomer-Resolved Spectroscopy.

Structural isomers, such as conformers or tautomers, are of significant importance across chemistry and biology, as they can have different functionalities. In gas-phase experiments using molecular beams, formation of many different isomers cannot be prevented, and their presence significantly complicates the assignment of spectral lines. Current isomer-resolved spectroscopic techniques heavily rely on theoretical calculations or make use of elaborate double-resonance schemes. We show here that isomer-resolved spectroscopy can also be performed using a single tunable laser. In particular, we demonstrate single-color isomer-resolved spectroscopy by utilizing electrostatic deflection to spatially separate the isomers. We show that for 3-aminophenol we can spatially separate the syn and anti conformers and use these pure samples to perform high-resolution REMPI spectroscopy, making the assignment of transitions to a particular isomer trivial, without any additional a priori information. This approach allows one to add isomer specificity to any molecular-beam-based experiment.

Mapping partial wave dynamics in scattering resonances by rotational de-excitation collisions.

One of the most important parameters in a collision is the 'miss distance' or impact parameter, which in quantum mechanics is described by quantized partial waves. Usually, the collision outcome is the result of unavoidable averaging over many partial waves. Here we present a study of low-energy NO-He collisions that enables us to probe how individual partial waves evolve during the collision. By tuning the collision energies to scattering resonances between 0.4 and 6 cm-1, the initial conditions are characterized by a limited set of partial waves. By preparing NO in a rotationally excited state before the collision and by studying rotational de-excitation collisions, we were able to add one quantum of angular momentum to the system and trace how it evolves. Distinct fingerprints in the differential cross-sections yield a comprehensive picture of the partial wave dynamics during the scattering process. Exploiting the principle of detailed balance, we show that rotational de-excitation collisions probe time-reversed excitation processes with superior energy and angular resolution.