Photoinitiated reactions in weakly bonded complexes

Wittig, C.; Sharpe, Steven W.; Beaudet, Robert A.

doi:10.1021/ar00153a004

Cited by 150 publications

(49 citation statements)

References 49 publications

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“…In the last two decades, different aspects concerning the formation of these clusters, and their effect on various physical and chemical processes occurring in the atmosphere, have attracted considerable interest. [1][2][3][4][5][6][7][8] This is not surprising, because there is a considerable amount of water in the atmosphere, especially in the troposphere.…”

Section: Introductionmentioning

confidence: 99%

“…Some aspects of the role of small water clusters (mainly 1:1 complexes) in atmospheric processes have been reviewed recently. [2,8] The role of water dimers in the atmosphere is an important-but still controversial-issue that has yet to be resolved.…”

Section: Introductionmentioning

confidence: 99%

“…O 3 ) in argon matrices and narrow band photolysis (l = 250 nm) of this reaction system have been studied by Jaeger [52] by means of Fourier transform infrared (FTIR) spectroscopy (see also Figures 7,8 and Table 1). The shifts observed for water modes upon complexation indicate that a very weak hydrogen bond was formed.…”

mentioning

confidence: 99%

“…In addition, a low-intensity feature appeared at 1100 cm À1 . Among these bands, the band at 2860 cm À1 was assigned to the n 2 + n 6 combination band of H 2 O 2 , although the DFT study also points out the possible small admixture of the IR vibrations of adsorption complexes between the ice surface and the HOOC and O( ) is currently thought to be the main contributor to the atmospheric production of hydroxyl radicals, see Equation (8). It is worthwhile to note that another possible source of hydroxyl radicals in the troposphere, the photolysis of the above-described ozone-water weakly bound complex [Equation (11)], has been investigated [61] …”

mentioning

confidence: 99%

“…Assuming the calculated rate constant of the complex H 2 O·O 3 photolysis and its electronic binding energy to be 10.0 kJ mol À1 , Frost and Vaida [61] estimated a five-fold reduction in the relative contribution of H 2 O·O 3 between the surface and 15 km altitude. A combined analysis of both channels of formation of HOC [bimolecular, Equation (8), and via the complex, Equation (11)], has shown that the calculated production of HOC from the photolysis of O 3 ·H 2 O complexes could represent a significant source of HOC in the troposphere.…”

mentioning

confidence: 99%

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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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