Understanding the origins of structure and bonding at the molecular level in complex chemical systems spanning magnitudes in length and time is of paramount interest in physical chemistry. We have coupled vibrational spectroscopy and X-ray based techniques with a series of microreactors and aerosol beams to tease out intricate and sometimes subtle interactions, such as hydrogen bonding, proton transfer, and noncovalent interactions. This allows for unraveling the self-assembly of arginine-oleic acid complexes in an aqueous solution and growth processes in a metal-organic framework. Terahertz and infrared spectroscopy provide an intimate view of the hydrogen-bond network and associated phase changes with temperature in neopentyl glycol. The hydrogen-bond network in aqueous glycerol aerosols and levels of protonation of nicotine in aqueous aerosols are visualized. Future directions in probing the hydrogen-bond networks in deep eutectic solvents and organic frameworks are described, and we suggest how X-ray scattering coupled to X-ray spectroscopy can offer insight into the reactivity of organic aerosols.

The properties of aerosols are of paramount importance in atmospheric chemistry and human health. The hydrogen bond network of glycerol-water aerosols generated from an aqueous solution with different mixing ratios is probed directly with X-ray photoelectron spectroscopy. The carbon and oxygen X-ray spectra reveal contributions from gas and condensed phase components of the aerosol. It is shown that water suppresses glycerol evaporation up to a critical mixing ratio. A dielectric analysis using terahertz spectroscopy coupled with infrared spectroscopy of the bulk solutions provides a picture of the microscopic heterogeneity prevalent in the hydrogen bond network when combined with the photoelectron spectroscopy analysis. The hydrogen bond network is composed of three intertwined regions. At low concentrations, glycerol molecules are surrounded by water forming a solvated water network. Adding more glycerol leads to a confined water network, maximizing at 22 mol %, beyond which the aerosol resembles bulk glycerol. This microscopic view of hydrogen bonding networks holds promise in probing evaporation, diffusion dynamics, and reactivity in aqueous aerosols.

A study of the formation of microstructures in the reaction of oleic acid with arginine elucidates dynamical self-assembly processes at the molecular level. Terahertz spectroscopy combined with density functional calculations reveals the initial hydrogen-bonding motifs in the assembly process, leading to the formation of micelles and vesicles. Small-angle X-ray scattering measurements allow for kinetic analysis of the growth processes of these nanostructures, revealing a prenucleation pathway of vesicles and micelles which lead to spongelike structures. This final stage of the assembly into spongelike aggregates is investigated with optical microscopy. The formed structures only occur at pH > 8 and are resistant to extreme acidic and basic conditions. A mechanistic pathway to the formation of the spongelike aggregates is described.

In the interstellar medium, diols and other prebiotic molecules adsorb onto icy mantles surrounding dust grains. Water in the ice may affect the reactivity and photoionization of these diols. Ethylene glycol (EG), 1,2-propylene glycol, and 1,3-propylene glycol clusters with water clusters were used as a proxy to study these interactions. The diol-water clusters were generated in a continuous supersonic molecular beam, photoionized by synchrotron-based vacuum ultraviolet light from the Advanced Light Source, and subsequently detected by reflectron time-of-flight mass spectrometry. The appearance energies for the detected clusters were determined from the mass spectra, collected at increasing photon energy. Clusters of both diol fragments and unfragmented diols with water were detected. The lowest energy geometry optimized conformers for the observed EG-water clusters and EG fragment-water clusters have been visualized using density functional theory (DFT), providing insight into hydrogen bonding networks and how these affect fragmentation and appearance energy. As the number of water molecules clustered around EG fragments (m/z 31 and 32) increased, the appearance energy for the cluster decreased, indicating a stabilization by water. This trend was supported by DFT calculations. Fragment clusters from 1,2-propylene glycol exhibited a similar trend, but with a smaller energy decrease, and no trend was observed from 1,3-propylene glycol. We discuss and suggest that the reactivity and photoionization of diols in the presence of water depend on the size of the diol, the location of the hydroxyl group, and the number of waters clustered around the diol.

Electronic excitation and concomitant energy transfer leading to Penning ionization in argon-acetylene clusters generated in a supersonic expansion are investigated with synchrotron-based photoionization mass spectrometry and electronic structure calculations. Spectral features in the photoionization efficiency of the mixed argon-acetylene clusters reveal a blue shift from the 2P1/2 and 2P3/2 excited states of atomic argon. Analysis of this feature suggests that excited states of argon clusters transfer energy to acetylene, resulting in its ionization and successive evaporation of argon. Theoretically calculated Arn (n = 2-6) cluster spectra are in excellent agreement with experimental observations, and provide insight into the structure and ionization dynamics of the clusters. A comparison between argon-acetylene and argon-water clusters reveals that argon solvates water better, allowing for higher-order excitons and Rydberg states to be populated. These results are explained by theoretical calculations of respective binding energies and structures.

Polyol-water clusters provide a template to probe ionization and solvation processes of paramount interest in atmospheric and interstellar chemistry. We generate glycerol water clusters in a continuous supersonic jet expansion and interrogate the neutral species with synchrotron-based tunable vacuum ultraviolet photoionization mass spectrometry. A series of glycerol fragments (m/z 44, 61, 62, and 74) clustered with water are observed. A judicious combination of backing pressure, nozzle temperature, and water vapor pressure allows for tuning the mol % of glycerol. The recorded appearance energies of the water cluster series m/z 62 and 74 are similar to that observed in pure glycerol, while the m/z 61 series shows a dependence on cluster composition. Furthermore, this series also tracks the water concentration of the beam. Theoretical calculations on neutral and ionized clusters visualize the hydrogen bond network in these water clusters and provide an assessment of the number of glycerol-glycerol, glycerol-water, and water-water hydrogen bonds in the cluster, as well as their interaction energies. This method of bond counting and interaction energy assessment explains the changes in the mass spectrum as a function of mol % and offers a glimpse of the disruption of the hydrogen bond network in glycerol-water clusters. The calculations also reveal interesting barrierless chemical processes in photoionized glycerol water clusters that are either activated or do not occur without the presence of water. Examples include spontaneous intramolecular proton transfer within glycerol to form a distonic ion, nonactivated breaking of a C-C bond, and spontaneous proton transfer from glycerol to water. These results appear relevant to radiation-induced chemical processing of alcohol-water ices in the interstellar medium.

A molecular-level understanding of phase changes in hydrogen-bonded solid-state systems is of great importance in fields spanning thermal science to medical therapeutics. Polyols have recently emerged as prime targets for deployment, given their versatility in phase-induced changes, and occupy a deep space in eutectic solvents. Here, we explore the hydrogen-bond network of neopentyl glycol (NPG) with terahertz time-domain spectroscopy, attenuated total reflection spectroscopy in the far- and mid-infrared regions augmented by electronic structure calculations. A picture emerges where vibrational spectroscopy can exquisitely probe a crystalline to amorphous solid-solid phase transition while spectroscopy in the mid-infrared region provides a molecular picture of the phase transition. These methods are then applied to understand the thermal properties and phase changes in NPG upon incorporation of bis(trifluoromethane)-sulfonimide lithium salt, to demonstrate that vibrational spectroscopy can directly probe the disruption of hydrogen-bond networks in plastic crystals.

The stability and distributions of small water clusters generated in a supersonic beam expansion are interrogated by tunable vacuum ultraviolet (VUV) radiation generated at a synchrotron. Time-of-flight mass spectrometry reveals enhanced population of various protonated water clusters (H⁺(H₂O)_n) based upon ionization energy and photoionization distance from source, suggesting there are "magic" numbers below the traditional n = 21 that predominates in the literature. These intensity distributions suggest that VUV threshold photoionization (11.0-11.5 eV) of neutral water clusters close to the nozzle exit leads to a different nonequilibrium state compared to a skimmed molecular beam. This results in the appearance of a new magic number at 14. Metadynamics conformer searches coupled with modern density functional calculations are used to identify the global minimum energy structures of protonated water clusters between n = 2 and 21, as well as the manifold of low-lying metastable minima. New lowest energy structures are reported for the cases of n = 5, 6, 11, 12, 16, and 18, and special stability is identified by several measures. These theoretical results are in agreement with the experiments performed in this work in that n = 14 is shown to exhibit additional stability, based on the computed second-order stabilization energy relative to most cluster sizes, though not to the extent of the well-known n = 21 cluster. Other cluster sizes that show some additional energetic stability are n = 7, 9, 12, 17, and 19. To gain insight into the balance between ion-water and water-water interactions as a function of the cluster size, an analysis of the effective two-body interactions (which sum exactly to the total interaction energy) was performed. This analysis reveals a crossover as a function of cluster size between a water-hydronium-dominated regime for small clusters and a water-water-dominated regime for larger clusters around n = 17.

Nucleation and crystallization arising from liquid to solid phase are involved in a multitude of processes in fields ranging from materials science to biology. Controlling the thermodynamics and kinetics of growth is advantageous to help tune the formation of complex morphologies. Here, we harness wide-angle X-ray scattering and vibrational spectroscopy to elucidate the mechanism for crystallization and growth of the metal-organic framework Co-MOF-74 within microscopic volumes enclosed in a capillary and an attenuated total reflection microchip reactor. The experiments reveal molecular and structural details of the growth processes, while the results of plane wave density functional calculations allow identification of lattice and linker modes in the formed crystals. Synthesis of the metal-organic framework with microscopic volumes leads to monodisperse and micron-sized crystals, in contrast to those typically observed under bulk reaction conditions. Reduction in the volume of reagents within the microchip reactor was found to accelerate the reaction rate. The coupling of spectroscopy with scattering to probe reactions in microscopic volumes promises to be a useful tool in the synthetic chemist's kit to understand chemical bonding and has potential in designing complex materials.

Polycyclic aromatic hydrocarbons (PAHs) are prevalent in deep space and on Earth as products in combustion processes bearing direct relevance to energy efficiency and environmental remediation. Reactions between hydrocarbon radicals in particular have been invoked as critical molecular mass growth processes toward cyclization leading to these PAHs. However, the mechanism of the formation of PAHs through radical - radical reactions are largely elusive. Here, we report on a combined computational and experimental study of the benzyl (C₇H₇) radical self-reaction to phenanthrene and anthracene (C₁₄H₁₀) through unconventional, isomer-selective excited state dynamics. Whereas phenanthrene formation is initiated via a barrierless recombination of two benzyl radicals on the singlet ground state surface, formation of anthracene commences through an exotic transition state on the excited state triplet surface through cycloaddition. Our findings challenge conventional wisdom that PAH formation via radical-radical reactions solely operates on electronic ground state surfaces and open up a previously overlooked avenue for a more "rapid" synthesis of aromatic, multi-ringed structures via excited state dynamics in the gas phase.