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Theoretical Characterization of the Gas‐Phase O 3 ⋅⋅⋅HO Hydrogen‐Bonded Complex
Author(s) -
Mansergas Alex,
Anglada Josep M.
Publication year - 2006
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.200600115
Subject(s) - chemistry , moiety , unpaired electron , gas phase , hydrogen , hydrogen bond , anharmonicity , computational chemistry , electronic structure , transition state , radical , crystallography , molecule , stereochemistry , organic chemistry , catalysis , physics , quantum mechanics
10.1002/cphc.200600115.abs We report a theoretical study on two gas‐phase hydrogen‐bonded complexes formed between ozone and hydroxyl radical that have relevance to atmospheric chemistry. This study was carried out by using CASSCF, CASPT2, QCISD, and CCSD(T) theoretical approaches in conjunction with the 6‐311+G(2df,2p) and aug‐cc‐pVTZ basis sets. Both complexes have a planar structure and differ from each other in the orientation of the electronic density of the unpaired electron associated with the HO radical moiety. Our calculations predict their stabilities to be 0.87 and 0.67 kcal mol −1 , respectively, at 0 K and show the importance of anharmonic effects in computing the red shift of the HO stretch originating from the hydrogen‐bonding interaction. We also report two transition states involving the movement of the HO moiety on the potential energy surfaces of these hydrogen‐bonded complexes.