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The kinetics of vibrationally excited OH(ν = 1) and OH(ν = 2) radicals was studied by time-resolved laser absorption in the overtone IR region. Two DFB laser diodes, 1509.3 and 1589 nm, were used. The technique allowed for the reliable study of the vibrational relaxation kinetics as well as the relative populations of the vibrationally excited states. The yields of OH(ν = 1) and OH(ν = 2) in the reaction O(1D) + H2O were determined. The rate constant of OH(ν = 1) relaxation in collision with water molecules was obtained ((9.2 ± 2.0) × 10−12 cm3/s). The dynamics of OH(ν = 1) and OH(ν = 2) populations were analyzed in detail, which made it possible to separately determine the relative contribution of the vibrational ladder relaxation channels OH(ν = 2) → OH(ν = 1) → OH(ν = 0) and the direct relaxation OH(ν = 2) → OH(ν = 0).

Monitoring excited hydroxyl (OH*) airglow is broadly used for characterizing the state and dynamics of the terrestrial atmosphere. Recently, the existence of excited hydroxyl was confirmed using satellite observations in the Martian atmosphere. The location and timing of its detection on Mars were restricted to a winter season at the north pole. We present three-dimensional global simulations of excited hydroxyl over a Martian year. The predicted spatio-temporal distribution of the OH* can provide guidance for future observations, namely by indicating where and when the airglow is likely to be detected.

Observations of excited hydroxyl (OH*) emissions are broadly used for inferring information about atmospheric dynamics and composition. We present several analytical approximations for characterizing the excited hydroxyl layer in the Martian atmosphere. They include the OH* number density at the maximum and the height of the peak, along with the relations for assessing different impacts on the OH* layer under night-time conditions. These characteristics are determined by the ambient temperature, atomic oxygen concentration, and their vertical gradients. The derived relations can be used for the analysis of airglow measurements and the interpretation of their variations.

The database of the SABER/TIMED satellite campaign includes the reconstruction results of nighttime distributions of O, H, and some other characteristics at heights of the mesosphere–lower thermosphere from measurements of volume emission rate ofOH* profiles near 2 μm, temperature, and ozone. The retrieval procedure is based on the chemical equilibrium approximation of nighttime ozone and a model of two excited OH states (ν = 9.8) forming the indicated radiation. In this work, a modernized model of these levels with the corrected constants corresponding to published data is used to retrieve O, H, OH, HO 2 , and the chemical heating rate at altitudes of 80–100 km according to SABER/TIMED measurements in 2002–2021. It is found that the new parameters of the retrieval procedure lead to significant (up to 2 times or more) changes in the spatial distributions of O, H, and chemical heating rate, but only a slight change in OH and HO 2 distributions.

Observations of vibrationally excited hydroxyl (OH*) emissions are widely used to obtain information on atmospheric dynamics and composition. In this paper, several analytical approximations are presented for characteristics of the hydroxyl layer in the Martian atmosphere, such as OH* concentrations at the maximum and the height of the maximum. Relationships are also given for estimating the influence of various factors on the OH* layer in nighttime conditions. These characteristics are determined by the ambient temperature and the concentration of atomic oxygen, including their vertical gradients. The obtained relationships are applied to the results of numerical modeling using the global atmospheric circulation model to predict the seasonal behavior of the hydroxyl layer on Mars. Based on the modeling data, the annual and intra-annual variations in the concentration of excited hydroxyl and the height of the OH* layer on Mars show both similarities to and considerable differences from those on Earth. The concentration and the height of the maximum in the equatorial, northern, and southern middle latitudes vary with the season, with the maximum concentrations and the lowest height being recorded in the first half of the year. Model calculations confirmed the presence of a peak in the OH* concentration in polar latitudes in winter at a height of approximately 50 km with volume emission densities of 2.1, 1.4, and 0.6 × 10 4 photons cm –3 s –1 for the transitions of vibrational levels 1–0, 2–1, and 2– 0, respectively. The resulting relationships can be used to analyze measurements and interpret their variations.

Observations of vibrationally excited hydroxyl (OH*) emissions are widely used to obtain information about the dynamics and composition of the atmosphere. We present some analytical approximations for the characteristics of the hydroxyl layer in the Martian atmosphere such as OH* concentration at the maximum and height of the maximum, as well as relations for estimating the influence of various factors on the OH* layer in night conditions. These characteristics depend on the temperature of the environment, concentration of atomic oxygen, and their vertical gradients. The relations are applied to the results of numerical modeling using the global atmospheric circulation model for prediction of seasonal behavior of the hydroxyl layer on Mars. Annual and intra-annual variations in the concentration of excited hydroxyl and layer height from the modeling data have both some similarities with those of the Earth and significant differences. The concentration and height maximum in the equatorial, northern and southern midlatitudes vary depending on the season; the maximum concentration and the minimum height fall on the first half of the year. Model calculations confirmed the presence of the peak OH* concentration at polar latitudes in winter at an altitude of approximately 50 km with the volume emission densities of 2.1, 1.4, and 0.6 × 10 4 photons cm –3 s –1 for vibrational level transitions 1–0, 2–1, and 2–0, respectively. The relations obtained may be used for the analysis of measurements and interpretation of their variations.

Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants – the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to  ∼  2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed, varying from < 10−20 µg m−3 for functionalized phenolic oligomers to > 10 µg m−3 for small open-ring species. The detection of abundant extremely low-volatile organic compounds (ELVOC) indicates that aqueous reactions of phenolic compounds are likely an important source of ELVOC in the atmosphere.

It is well known that biological systems, such as microorganisms, plants, and animals, including human beings, form spontaneous electronically excited species through oxidative metabolic processes. Though the mechanism responsible for the formation of electronically excited species is still not clearly understood, several lines of evidence suggest that reactive oxygen species (ROS) are involved in the formation of electronically excited species. This review attempts to describe the role of ROS in the formation of electronically excited species during oxidative metabolic processes. Briefly, the oxidation of biomolecules, such as lipids, proteins, and nucleic acids by ROS initiates a cascade of reactions that leads to the formation of triplet excited carbonyls formed by the decomposition of cyclic (1,2-dioxetane) and linear (tetroxide) high-energy intermediates. When chromophores are in proximity to triplet excited carbonyls, the triplet-singlet and triplet-triplet energy transfers from triplet excited carbonyls to chromophores result in the formation of singlet and triplet excited chromophores, respectively. Alternatively, when molecular oxygen is present, the triplet-singlet energy transfer from triplet excited carbonyls to molecular oxygen initiates the formation of singlet oxygen. Understanding the mechanism of the formation of electronically excited species allows us to use electronically excited species as a marker for oxidative metabolic processes in cells.

Bisphenol A (BPA) is regarded as a hazardous pollutant that exists widely in aquatic environments, posing a severe threat to human health. In this study, a vacuum ultraviolet (VUV) lamp emitting a hybrid of 254 nm and 185 nm light was used to degrade BPA. Results indicated that photolysis via 254 nm wavelength accounted for 24.93% for BPA decay, while indirect oxidation was responsible for 52.27% of decay. Results confirmed that the degradation of BPA under VUV illumination mainly occurred via photo-excited degradation and ·OH electrophilic addition reactions based on average local ionization energy (ALIE) calculation and density functional theory (DFT) calculations. Therefore, only light with a wavelength of 254 nm was able to induce the first three excited states of BPA, forming the electron transition type of n → π* from O atom to a single benzene ring and π → π* in the single benzene ring. Indirect oxidation by ·OH occurred as it preferentially attacked the C6 atom in BPA ring A. Moreover, the energy required for photo-excited degradation was about twofold than that of ·OH electrophilic addition reactions.

This paper summarizes significant progress in quantifying organic substituent effects in the last 20 years. The main content is as follows： （1） The principle of electronegativity equalization has gained wide acceptance, and has been used to calculate the intramolecular charge distribution and inductive effect of groups. A valence electrons equalization method was proposed to compute the molecular electronegativity on the basis of geometric mean method, harmonic mean method, and weighted mean method. This new calculation method further extended the application of the principle of electronegativity equalization. （2） A scale method was established for experimentally determining the electrophilic and nucleophilic ability of reagents, in which benzhydryliumions and quinone methides were taken as the reference compounds, and the research field was extended to the gas phase conditions, organometallic reaction and radicals system. Moreover, the nucleophilicity parameters N and electro- philicity parameters E for a series of reagents were obtained. The definition and quantitative expression of electrophilicity in- dex co and nucleophilicity index co were proposed theoretically, and the correlation between the parameters from experimental determination and the indexes from theoretical calculation was also investigated. （3） The polarizability effect parameter was initially calculated by empirical method and further developed by quantum chemistry method. Recently, the polarizability ef- fect index of alkyl （PEI） and groups （PEIx） were proposed by statistical method, and got wide applications in explaining and estimating gas-phase acidity and basicity, ionization energy, enthalpy of formation, bond energy, reaction rate, water solubility and chromatographic retention for organic compounds. （4） The excited-state substituent constant Crcc obtained directly from the UV absorption energy data of substituted benzenes, is different from the polar constants in molecular ground state and the radical spin-delocalization effects constants in molecular radical state. The proposed constant Crcc correlated well with the UV absorption energy of many kinds of organic compounds, such as 1,4-disubstituted benzenes, substituted stilbenes, and di- substituted N-benzylidenebenzenamine. （5） The establishment of the steric shielding effect distinguished the three traditional steric effects. The stereoselectivity index Ci was proposed to quantify the stereoselectivity of the addition reaction of carbonyl with nucleophilic reagent. The shielding parameter Rs was defined to quantitatively express the specific surface of the reac- tion center screened by a group. Further, the Topological Steric Effect Index （TSEI） of a group was proposed on the basis of the relative specific volume of reaction center screened by the atoms of substituents. These parameters can be applied in esti- mating the intramolecular dihedral angles, stereoselectivity of reaction, enthalpies of formation of alkenes and alkylbenzene, acidity of substitutedimidazolium ionic liquid, and the reaction rate of alkane and hydroxyl radical. In addition, some sugges- tions and prospects for further studies on quantifying the organic substituent effects were presented in this paper.