Theoretical studies of atmospheric water complexes
Intermolecular complexes between H{sub 2}O and atmospheric species HO, HO{sub 2}, H{sub 2}O{sub 2}, O{sub 3}, NO and NO{sub 2} have been studied by ab initio molecular orbital methods. The studies have been performed to the MP2 theory level by using 4-31G, 6-31G, D95, 6-31G{sup **}, D95{sup **}, 6-311G{sup **}, 6-311 + G{sup **}, 6-311 ++ G{sup **}, 6-311 + G(2d,1p) and 6-311 + G(2d,2p) basic sets. The geometries were fully optimized. The vibrational frequencies were calculated. The Basis Set Superposition Error (BSSE) were estimated. Finally, the binding energies of the complexes were predicted with other thermochemical properties. The binding energies of H{sub 2}O{center_dot}HO, H{sub 2}O{center_dot}HO{sub 2}, H{sub 2}O{center_dot}H{sub 2}O{sub 2}, H{sub 2}O{center_dot}O{sub 3}, H{sub 2}O{center_dot}NO, and H{sub 2}O{center_dot}NO{sub 2} are estimated to be 5.7 {+-} 0.6, 8.9 {+-} 1.0, 7.3 {+-} 1.3, 1.8 {+-} 0.2, 1.17 (no BSSE correction) and 2.98 (no BSSE correction) Kcal/Mol, respectively. The K{sub eq} for dimerization to yield H{sub 2}O{center_dot}HO, H{sub 2}O{center_dot}HF, H{sub 2}O{center_dot}HO{sub 2}, H{sub 2}O{center_dot}H{sub 2}O and H{sub 2}O{center_dot}H{sub 2}O{sub 2} are estimated to be 0.11, 2.8, 3.3, 0.067 and 0.11 atm{sup {minus}1}, respectively. The H{sub 2}O{center_dot}HO, H{sub 2}O{center_dot}H{sub 2}O and H{sub 2}O{center_dot}H{sub 2}O{sub 2} are quite strongly bonded complexes, while H{sub 2}O{center_dot}O{sub 3}, H{sub 2}O{center_dot}NO and H{sub 2}O{center_dot}NO{sub 2} are quite strongly bonded complexes. The K{sub eq} changes with temperature are discussed, and their importance in atmospheric chemistry are addressed.
- Research Organization:
- Portland State Univ., OR (United States)
- OSTI ID:
- 113785
- Resource Relation:
- Other Information: TH: Thesis (Ph.D.); PBD: 1992
- Country of Publication:
- United States
- Language:
- English
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