Rapid N2O Formation from N2 on Water Droplet Surfaces.

Nitrogen (N2) has long been considered as stable atmospheric reservoir for N element and has a persistence time of hundreds of years. This study reveals that oxygen (O2) at typical tropospheric concentrations can rapidly activate N2, leading to substantial production of nitrous oxide (N2O), the third most impactful greenhouse gas, at rates approaching 2.83 ± 0.

Heterogenous Chemistry of IO as a Critical Step in Iodine Cycling.

Global iodine emissions have been increasing rapidly in recent decades, further influencing the Earth's climate and human health. However, our incomplete understanding of the iodine chemical cycle, especially the fate of higher iodine oxides, introduces substantial uncertainties into atmospheric modeling. IO was previously deemed a "dead end" in iodine chemistry; however, we provide atomic-level evidence that IO can undergo rapid air-water or air-ice interfacial reactions within several picoseconds; these reactions are facilitated by prevalent chemicals on seawater such as amines and halide ions, to produce photolabile reactive iodine species such as HOI and IX (X = I, Br, and Cl).

Promoting ClO Generation from the HOCl + HOCl Reaction on Aqueous/Frozen Air-Water Interfaces.

Hypochlorous acid (HOCl) is considered a temporary reservoir of dichlorine monoxide (ClO). Previous studies have suggested that ClO is difficult to generate from the reaction of HOCl + HOCl in the gas phase. Here, we demonstrate that ClO can be generated from the HOCl + HOCl reaction at aqueous/frozen air-water interfaces, which is confirmed by ab initio molecular dynamic calculations.

Tunable Topological Wetting State of Water Droplets on Planar Surfaces: Closed-Loop Chemical Heterogeneity by Design.

Understanding droplet wetting on surfaces has broad implications for surface science and engineering. Here, we report a joint theoretical/experimental study of the topological wetting states of water droplets on chemically heterogeneous closed-loop and planar surfaces. Interestingly, we provide both simulation and experimental evidence of biloop or even multiloop transition wetting states of water droplets.

Hydrogen-Bonded Complexes of HPN⋅ and HNP⋅ Radicals with Carbon Monoxide.

Phosphorus mononitride (PN) is a carrier of phosphorus in the interstellar medium. As the simplest derivatives of PN, the radical species HPN⋅ and HNP⋅ have remained elusive. Herein, we report the generation, characterization, and photochemistry of HPN⋅ and HNP⋅ in N-matrix at 3 K.

Time Resolved Quantum Tomography in Molecular Spectroscopy by the Maximal Entropy Approach.

Attosecond science offers unprecedented precision in probing the initial moments of chemical reactions, revealing the dynamics of molecular electrons that shape reaction pathways. A fundamental question emerges: what role, if any, do quantum coherences between molecular electron states play in photochemical reactions? Answering this question necessitates quantum tomography─the determination of the electronic density matrix from experimental data, where the off-diagonal elements represent these coherences. The Maximal Entropy (MaxEnt) based Quantum State Tomography (QST) approach offers unique advantages in studying molecular dynamics, particularly with partial tomographic data.

Neighboring Catalytic Sites Are Essential for Electrochemical Dechlorination of 2-Chlorophenol.

The electrocatalytic reduction process is a promising technology for decomposing chlorinated organic pollutants in water but is limited by the lack of low-cost catalysts that can achieve high activity and selectivity. In studying electrochemical dechlorination of 2-chlorophenol (2-CP) in aqueous media, we find that cobalt phthalocyanine molecules supported on carbon nanotubes (CoPc/CNT), which is a highly effective electrocatalyst for breaking the aliphatic C-Cl bonds in 1,2-dichloroethane (DCA) and trichloroethylene (TCE), are completely inactive for reducing the aromatic C-Cl bond in 2-CP. Detailed mechanistic investigation, including volcano plot correlation between dechlorination rate and atomic hydrogen adsorption energy on various transition metal surfaces, kinetic measurements, in situ Raman spectroscopy, and density functional theory calculations, reveals that the reduction of the aromatic C-Cl bond in 2-CP goes through a hydrodechlorination mechanism featuring a bimolecular reaction between adsorbed atomic hydrogen and 2-CP on the catalyst surface, which requires neighboring catalytic sites, whereas the aliphatic C-Cl bonds in DCA and TCE are cleaved by direct electron transfer from the catalyst, which can occur on isolated single sites.

Hydrate Technologies for CO Capture and Sequestration: Status and Perspectives.

CO capture and sequestration based on hydrate technology are considered supplementary approaches for reducing carbon emissions and mitigating the greenhouse effect. Direct CO hydrate formation and CH gas substitution in natural gas hydrates are two of the main methods used for the sequestration of CO in hydrates. In this Review, we introduce the crystal structures of CO hydrates and CO-mixed gas hydrates and summarize the interactions between the CO molecules and clathrate hydrate/HO frames.

Direct Visualization of Molecular Stacking in Quasi-2D Hexagonal Ice.

Understanding ice nucleation and growth is of great interest to researchers due to its importance in the biological, cryopreservation, and environmental fields. However, microstructural investigations of ice on the molecular scale are still lacking. In this paper, a simple method is proposed to prepare quasi-2-dimensional ice I films, which have been characterized via cryogenic transmission electron microscope.

Mechanistic Insights into NO-Halide Ions Chemistry at the Air-Water Interface.

The activation of halogens (X = Cl, Br, I) by NO is linked to NO sources, ozone concentrations, NO reactivity, and the chemistry of halide-containing aerosol particles. However, a detailed chemical mechanism is still lacking. Herein, we explored the chemistry of the NO···X systems at the air-water interface.

Overlooked significance of iodic acid in new particle formation in the continental atmosphere.

New particle formation (NPF) substantially affects the global radiation balance and climate. Iodic acid (IA) is a key marine NPF driver that recently has also been detected inland. However, its impact on continental particle nucleation remains unclear.

Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface.

Chlorine oxides play crucial roles in ozone depletion, and the final oxidation steps of chlorine oxide potentially result in the formation of chloric acid (HClO) or perchloric acid (HClO). Herein, the solvation and reactive uptake of three stable isomers of chlorine trioxide (ClO), namely, ClOCl(O)O, ClClO, and ClOOOCl, at the air-water interface were investigated using classical and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) coupled with advanced free energy methods. Two distinct mechanisms were revealed for the hydrolysis of ClOCl(O)O and ClClO: molecular and ionic mechanisms.

Direct Observation of HOON Intermediate in the Photochemistry of HONO.

The photochemistry of nitrous acid (HONO), encompassing dissociation into OH and NO as well as the reverse association reaction, plays a pivotal role in atmospheric chemistry. Here, we report the direct observation of nitrosyl--hydroxide (HOON) in the photochemistry of HONO, employing matrix-isolation IR and UV-vis spectroscopy. Despite a barrier of approximately 30 kJ/mol, HOON undergoes spontaneous rearrangement to the more stable HONO isomer through quantum mechanical tunneling, with a half-life of 28 min at 4 K.

Spontaneous Molecular Bromine Production in Sea-Salt Aerosols.

Bromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea-salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br) by O and HO in the absence of additional oxidants.

Water-Catalyzed Formation of Reactive Oxygen Species from NO on a Weakly Hydrated Calcite Surface.

The interfaces of weakly hydrated mineral substrates have been shown to serve as catalytic sites for chemical reactions that may not be accessible in the gas phase or under bulk conditions. Currently known mechanisms for the formation of reactive oxygen species (ROS) from nitrogen dioxide (NO) involve NO dimerization. Here, we report the formation of the ROS HONO via a mechanism involving simple adsorption of a single NO molecule on a weakly hydrated calcite substrate.

Rovibrational analysis of AlCO3, OAlO2, and HOAlO2 for possible atmospheric detection.

The lack of observational data for the AlO molecule in the mesosphere/lower thermosphere may be due to ablated aluminum reacting quickly to form other species. Previously proposed reaction pathways show that aluminum could be ablated in the atmosphere from meteoritic activity, but there currently exist very limited spectroscopic data on the intermediates in these reactions, limiting the possible detection of said molecules. As such, rovibrational spectroscopic data are computed herein using quartic force field methodology at four different levels of theory for the neutral intermediates AlCO3, OAlO2, and HOAlO2.

Formation of compounds with diverse polyelectrolyte morphologies and nonlinear ion conductance in a two-dimensional nanofluidic channel.

Aqueous electrolytes subjected to angstrom-scale confinement have recently attracted increasing interest because of their distinctive structural and transport properties, as well as their promising applicability in bioinspired nanofluidic iontronics and ion batteries. Here, we performed microsecond-scale molecular dynamics simulations, which provided evidence of nonlinear ionic conductance under an external lateral electric field due to the self-assembly of cations and anions with diverse polyelectrolyte morphologies (, extremely large ion clusters) in aqueous solutions within angstrom-scale slits. Specifically, we found that the cations and anions of LiSO and CaSO formed chain-like polyelectrolyte structures, whereas those of NaSO and MgSO predominantly formed a monolayer of hydrated salt.

Charge Redistribution in Mechanochemical Reactions for Solid Interfaces.

Mechanochemical strategies are widely used in various fields, ranging from friction and wear to mechanosynthesis, yet how the mechanical stress activates the chemical reactions at the electronic level is still open. We used first-principles density functional theory to study the rule of the stress-modified electronic states in transmitting mechanical energy to trigger chemical responses for different mechanochemical systems. The electron density redistribution among initial, transition, and final configurations is defined to correlate the energy evolution during reactions.

Exploring the photochemistry of OAlOH: Photodissociation pathways and electronic spectra.

This study was focused on the photochemistry of OAlOH and three possible pathways, which were studied with high-level multireference configuration interaction ab initio calculations. We computed cuts of the six-dimensional potential energy surfaces for the ground, the lowest singlet and triplet excited states, and probed the photodissociation mechanisms and the stabilities. The OAlOH electronic spectrum, with an energy reaching 7.

Two-dimensional ice-like water adlayers on a mica surface with and without a graphene coating under ambient conditions.

Water tends to wet all hydrophilic surfaces under ambient conditions, and the first water adlayers on solids are important for a broad range of physicochemical phenomena and technological processes, including corrosion, wetting, lubrication, anti-icing, catalysis, and electrochemistry. Unfortunately, challenges in characterizing the first water adlayer in the laboratory have hampered molecular-level understanding of the contact water structure. Herein, we present the first molecular dynamics simulation evidence of a previously unreported ice-like adlayer structure (named as Ice-AL-II) on a prototype mica surface under ambient conditions.

Triplet State Radical Chemistry: Significance of the Reaction of SO with HCOOH and HNO.

The triplet excited states of sulfur dioxide can be accessed in the UV region and have a lifetime large enough that they can react with atmospheric trace gases. In this work, we report high level ab initio calculations for the reaction of the aB and bA excited states of SO with weak and strong acidic species such as HCOOH and HNO, aimed to extend the chemistry reported in previous studies with nonacidic H atoms (water and alkanes). The reactions investigated in this work are very versatile and follow different kinds of mechanisms, namely, proton-coupled electron transfer () and conventional hydrogen atom transfer () mechanisms.