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Photochemical Water Decomposition in the Troposphere: DFT Study with a Symmetrized Kohn–Sham Formalism
Author(s) -
Minaev Boris F.,
Zakharov Ivan I.,
Zakharova Olga I.,
Tselishtev Alexei B.,
Filonchook Anton V.,
Shevchenko Alexandr V.
Publication year - 2010
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.201000440
Subject(s) - excited state , chemistry , photochemistry , radical , troposphere , density functional theory , molecule , photodissociation , formalism (music) , ground state , computational chemistry , atomic physics , physics , meteorology , organic chemistry , art , musical , visual arts
Photochemical reaction of the electronically excited NO 2 * species with the water molecule is studied in terms of a new version of density functional theory by selecting the specific 2 A′′ symmetry of the whole system, which is different from the ground‐state pattern. The excited ${{\rm{\tilde C}}}$ 2 A 2 state of the NO 2 molecule is found to be distorted to the equilibrium structure ONO . , which poses the 2 A′′ symmetry in the C s point group. With the B3LYP functional it is shown that such an electronically excited NO 2 * molecule, generated by visible light ( λ =420 nm), can react with water vapor to produce OH+HONO species, an important source of tropospheric hydroxyl radicals. This photochemical process can be considered as a possible mechanism of atmosphere self‐cleaning.