Atmospheric Significance of Water Clusters and Ozone–Water Complexes

Abstract

Ozone-water complexes O3···(H2O)n (n = 1-4) have been theoretically investigated using QCISD and CCSD(T) methods along with the 6-311G(2df,2p), 6-311+G(2df,2p), aug-cc-pVDZ, aug-cc-pVTZ, and aug-cc-pVQZ basis sets and extrapolation to CBS limit. For comparison, water clusters (H2O)n (n = 1-4) have also been studied at the same level of theory. The ozone-water complexes are held together by a combination of weak specific hydrogen-bonding and van der Waals interactions. Surprisingly, the hydrogen-bonded complexes are not necessarily the most stable ones. In particular, in the most stable 1:1 complex structure the main stabilizing factors come from van der Waals interactions. The high accuracy of the calculated binding energies provides a reliable basis to discuss the abundance of these clusters in the atmosphere. We predict concentrations up to 9.24 × 10(15), 3.91 × 10(14), and 2.02 × 19(14) molecules·cm(-3) for water dimer, trimer, and tetramer in very hot and humid conditions and that the concentrations of these clusters would remain significant up to 10 km of altitude in the Earth's atmosphere. The concentration of O3···H2O is predicted to be between 1 and 2 orders of magnitude higher than previous estimation from the literature: up to 5.74 × 10(8) molecules·cm(-3) in very hot and humid conditions at ground level and up to 1.56 × 10(7) molecules·cm(-3) at 10 km of altitude of the Earth's atmosphere. The concentrations of the other ozone-water clusters, O3··(H2O)2, O3···(H2O)3, and O3···(H2O)4, are predicted to be very small or even negligible in the atmosphere.

An exploration of the ozone dimer potential energy surface

“…There have been a small number of studies which employed more appropriate methodologies, e.g., quadratic configuration interaction with single and double excitations (QCISD), coupled-cluster with singles and doubles and linked triples (CCSD(T)), and/or multi-configurational methods, 13,14 but most of these have focused on complexes between O 3 and H 2 O. [15][16][17] Within the experimental context, in their study of the O· · ·O 3 complex through O 3 generation with photolysis of an oxygen matrix at 11 K, Schriver-Mazzuoli et al observed a peak at λ = 360 nm for the photodissociation of the (O 3 ) 2 dimer, but did not provide any structure. 18 Later, in 2001, Bahou et al 19 studied the IR spectroscopy and photochemistry at 266 nm of (O 3 ) 2 trapped in an argon matrix and cona) Author to whom correspondence should be addressed.…”

Formation Mechanism of Atmospheric Ammonium Bisulfate: Hydrogen‐Bond‐Promoted Nearly Barrierless Reactions of SO3 with NH3 and H2O

“…The above studies focused on the reactions without a surrounding molecule and with only one surrounding molecule. Thus, through AIMD simulations, we further investigated the cases with multiple water molecules to account for the reactions occurring in clusters and droplets in the atmosphere . The reactions with 3–5 and 34 H 2 O molecules were studied successively, and all the reactions leading to the formation of NH 4 HSO 4 were observed soon after starting each simulation.…”

Hydrogen Peroxide Insular Dodecameric and Pentameric Clusters in Peroxosolvate Structures

“…Hydrogen-bondedsmall-moleculeclustersinthegas,liquid, and solid states have been studied extensively because they play asignificant role in various chemical, environmental, and biological processes,a nd the greatest interest is attracted by clusters of water as the most important biological molecule. [1][2][3][4][5][6][7] Among other tiny molecular species hydrogen peroxide is the closest relative of water and is also involved in many significant environmental and biological phenomena. [8][9][10] It was recently shown that hydrogen peroxide forms noticeably stronger H-bonds than water in isomorphous peroxosolvates-hydrates.…”