Crossed Molecular Beam Study of the Reaction Cl + O₃

Abstract

The reaction of ground-state ( 2 P J ) chlorine atom with ozone molecule was studied by the crossed molecular beams technique at four different center-of-mass (CM) collision energies ranging from 6 to 32 kcal/mol. CM translational energy and angular distributions of the products were derived from experimental measurements. A significant fraction of the total available energy is channeled into the products' translation, and the ClO product is sideways and forward scattered with respect to the Cl atom. Product translational energy release depends on the CM scattering angle, with higher values at small CM angles. With the increase of collision energy, product translational energy increases, and the ClO product is scattered to a more forward direction. The reaction Cl + O 3 proceeds through a direct reaction mechanism. The Cl atom is most likely to attack the terminal oxygen atom of the ozone molecule.

Quantum chemical study of the reaction mechanism of ozone and methane with fluorine and chlorine atoms

“…Because the reaction of Cl ϩ O 3 is known to predominantly give only the ground-state ClO( 2 ⌸) ϩ O 2 ( 3 ⌺ Ϫ g) [11] products, we consider here only one reaction pathway. Along the path, full geometry optimizations were run to the stationary points (intermediates and transition states) at the MP2 (full)/6-31G* level of the G3 and G3MP2 methods.…”

CROSSED-BEAM STUDIES OF REACTION DYNAMICS

“…In Berkeley, an impressive amount of work with the classic CMB technique has been carried out on reactions of oxygen atoms (205,206), alkali (207,208) and alkali-earth ground and electronically excited atoms (136,137), halogen atoms (209)(210)(211), and also, more recently, carbon atoms (212)(213)(214). Of particular interest are the reactions of Cl and Br with O 3 (210,211), which are of fundamental importance in stratospheric chemistry.…”

Ab initio study on the reaction mechanism of ozone with the chlorine atom

“…Since the ClϩO 3 is known to predominantly give only the ground state ClO͑ 2 ⌸͒ϩO 2 ( 3 ⌺ g Ϫ ) products, 6 we consider here only the ground electronic state potential energy surface. On this surface, full geometry optimizations were run to locate all the stationary points at the HF/6-31G(d), MP2/6-31G(d), MP2/6-311G(d), 18 as well as QCISD/ 6-311G(d) ͑Ref.…”

“…The reaction ClϩO 3 →ClOϩO 2 is of fundamental importance in stratosphere chemistry. [6][7][8] Chlorine trioxides have been postulated as a reaction intermediate. [9][10][11][12][13][14][15] A direct reaction without intermediate was also proposed from calculations at a semiempirical level.…”