Radical–Molecule Complexes: Changing Our Perspective on the Molecular Mechanisms of Radical–Molecule Reactions and their Impact on Atmospheric Chemistry

Hansen, Jaron C.; Francisco, Joseph S.

doi:10.1002/1439-7641(20021018)3:10<833::aid-cphc833>3.0.co;2-0

Cited by 95 publications

(73 citation statements)

References 34 publications

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“…First, weak atmospheric complexes can play a significant role, even when their concentration and, hence, their ability to absorb solar radiation is small. [2,25,[58][59][60] They cannot remarkably affect the radiation balance of the atmosphere. However, the reactions of the complexes induced by sunlight can have a remarkable effect on the formation of photochemically active radicals in the atmosphere.…”

Section: Complexes Of H 2 O With Radicals (Hoc Hooc Hoooc)mentioning

confidence: 99%

Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H₂O Complexes with Oxidants

Сенников¹,

Ignatov²,

Schrems³

2005

ChemPhysChem

100

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Experimental observations and data from quantum chemical calculations on complexes between water molecules and small, oxygen‐containing inorganic species that play an important role as oxidants in the atmosphere (O(1D), O(3P), O2(X3Σg), O2(b1Σg+), O3, HO, HOO, HOOO, and H2O2) are reviewed, with emphasis on their structure, hydrogen bonding, interaction energies, thermodynamic parameters, and infrared spectra. In recent years, weakly bound complexes containing water have increasingly attracted scientific attention. Water in all its phases is a major player in the absorption of solar and terrestrial radiation. Thus, complexes between water and other atmospheric species may have a perceivable influence on the radiative balance and contribute to the greenhouse effect, even though their concentrations are low. In addition, they can play an important role in the chemistry of the Earth's atmosphere, particularly in the oxidation of trace gases. Apart from gas‐phase complexes, the interactions of oxidants with ice surfaces have also received considerable advertency lately due to their importance in the chemistry of snow, ice clouds, and ice surfaces (e.g., ice shields in polar regions). In paleoclimate—respectively paleoenvironmental—studies, it is essential to understand the transfer processes from the atmosphere to the ice surface. Consequently, special attention is being paid here to the intercomparison of the properties of binary complexes and the complexes and clusters of more complicated compositions, including oxidants adsorbed on ice surfaces, where ice is considered a kind of large water cluster. Various facts concerning the chemistry of the Earth's atmosphere (concentration profiles and possible influence on radical reactions in the atmosphere) are discussed.

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Section: Complexes Of H 2 O With Radicals (Hoc Hooc Hoooc)mentioning

confidence: 99%

Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H₂O Complexes with Oxidants

Сенников¹,

Ignatov²,

Schrems³

2005

ChemPhysChem

100

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“…Reaction (1) is anticipated to proceed via H-atom abstraction. There are several examples in the recent chemical kinetic literature revealing that many of the hydrogen abstraction reactions of OH radicals proceed via the formation of hydrogen-bonded 'prereaction' complexes (PRCs) which frequently give rise to specific kinetic features, such as a pressure dependence and unusual temperature dependence (see, e.g., the review papers of [28][29] and [30]). In a very recent theoretical article, Simmie has reported on the kinetics, mechanism and thermochemistry of the reactions of cyclic ethers with different free radicals including the reaction of OH with 2-MTHF [31].…”

Section: Determination Of K 1 From Rr-gc Experimentsmentioning

confidence: 99%

Direct and relative rate coefficients for the gas-phase reaction of OH radicals with 2-methyltetrahydrofuran at room temperature

Illés

Zügner

et al. 2016

Reac Kinet Mech Cat

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2-methyltetrahydrofuran (2-MTHF) is a renewable green solvent, a platform molecule for organic syntheses and a potential automotive fuel or fuel additive that can be produced efficiently from lignocellulosic biomass. Its reaction with OH radicals is important concerning both of its atmospheric fate and combustion. Kinetics of the overall reaction OH + 2-MTHF → products (1) were studied at room temperature (T = 298 ± 1 K) using both direct and relative kinetic methods. The low pressure fast discharge flow (DF) experiments coupled with resonance fluorescence (RF) detection of OH have provided the direct rate coefficient of k 1 (298 K, 2.64 mbar He) = (1.21 ± 0.14 (±2σ)) × 10 -11 cm 3 molecule -1 s -1 . The relative-rate experiments (RR) with gas-chromatographic (GC) analysis were performed at higher pressure in synthetic air using the reaction OH + cyclohexane (c-C 6 H 12 ) → products (2) as reference. The determined rate coefficient ratio k 1 /k 2 = 3.80 ± 0.17 (±2σ) has been converted to k 1 (298 K, 1030 mbar air) = (2.65 ± 0.55 (±2σ)) × 10 -11 cm 3 molecule -1 s -1 . This k 1 value agrees reasonably well with the only other rate coefficient reported which was determined also at higher pressures. Comparison with the DF result indicates a possible pressure dependence of the reaction. Impact of 2-MTHF on the chemistry of the atmosphere has been briefly discussed.

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“…Recent studies have revealed that adsorbed water on the surface of aerosols in the troposphere affects heterogeneous reactions between radicals and aerosol particles (Park et al, 2008). Adsorbed water can also interfere with gaseous reactions in the troposphere by removing or blocking one or more of the reactants (Sennikov et al, 2005;Hansen and Francisco, 2002;Aloisio and Francisco, 2000). Due to its ability to form hydrogen bonds, water vapor clusters readily with various gaseous species.…”

Section: Introductionmentioning

confidence: 99%

Ab initio Study on the Complex Forming Reaction of OH and H2O in the Gas Phase

Park¹

2015

Asian J. Atmos. Environ

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The estimation of the concentration of hydroxyl radical (OH) in the atmosphere is essential to build atmospheric models and to understand the mechanisms of the reactions involved in OH. Although water vapor is one of the most abundant species in the troposphere, only a few studies have been performed for the reaction of OH and water vapor. Here I demonstrate an ab initio study on the complex forming reation of OH with H 2 O in the gas phase performed based on density functional theory to calculate the reaction rate and the energy states of the reactant and the OH-H 2 O complex. The structure of the complex, which belongs to the Cs point group, was optimized at global minima. The transition state was not found at the B3LYP and MP2 levels of theory. Rate constants of the forward and the reverse reactions were calculated as 1.1 × 10 -16 cm 3 molecule -1 s -1 and 5.3 × 10 9 s -1 , respectively. The extremely slow rates of complex forming reaction and the resulting hydrogen atom exchange reaction of OH and H 2 O, which are consistent with experimentally determined values, imply a negligible possibility of a change in OH reactivity through the title reaction.

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Radical–Molecule Complexes: Changing Our Perspective on the Molecular Mechanisms of Radical–Molecule Reactions and their Impact on Atmospheric Chemistry

Cited by 95 publications

References 34 publications

Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H₂O Complexes with Oxidants

Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H₂O Complexes with Oxidants

Direct and relative rate coefficients for the gas-phase reaction of OH radicals with 2-methyltetrahydrofuran at room temperature

Ab initio Study on the Complex Forming Reaction of OH and H2O in the Gas Phase

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Radical–Molecule Complexes: Changing Our Perspective on the Molecular Mechanisms of Radical–Molecule Reactions and their Impact on Atmospheric Chemistry

Cited by 95 publications

References 34 publications

Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H2O Complexes with Oxidants

Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H2O Complexes with Oxidants

Direct and relative rate coefficients for the gas-phase reaction of OH radicals with 2-methyltetrahydrofuran at room temperature

Ab initio Study on the Complex Forming Reaction of OH and H2O in the Gas Phase

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Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H₂O Complexes with Oxidants

Complexes and Clusters of Water Relevant to Atmospheric Chemistry: H₂O Complexes with Oxidants