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

Abstract

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.

Experimental Study on the Interference of Water Vapor on the Chemical Ionization of OH by Sulfur Hexafluoride Ion

“…The peak intensities of SF 4 Figure 2(b) shows that the intensity of the OH peak decreased with the addition of water into the flow tube system, which was due to not only the loss of CIMS sensitivity as described above, but also to the conversion of OH into OH-water complexes. [17][18][19][20] In particular, the peak intensity of [OH(…”

On the Role of Water in Heterogeneous Catalysis: A Tribute to Professor M. Wyn Roberts

“…However, IR spectra and computational studies suggest that the H 2 O-O 2 complex is hydrogen bonded [47] (Fig. 9) rather than T shaped as in the case of ammonia dioxygen.…”

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

“…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.…”

“…No clear experimental evidence corroborates for the existence of such a complex, although theoretical studies have estimated its structure and energy (Karakus and Ozkan, 2005;Sennikov et al, 2005;Aloisio and Francisco, 2000;Wang et al, 1999;Dubey et al, 1997;Kim et al, 1991). Little is known of the rate constant and mechanism of the complex forming reaction of OH and H 2 O.…”