We report full quantum cross sections and rate constants for the (18)O + (36)O2 → (36)O2 + (18)O collision process. This constitutes to the best of our knowledge the first dynamical study of the (18)O(18)O(18)O system, with three identical (18)O oxygen atoms. We emphasize the comparison with the (16)O + (32)O2 collision as this latter presents the exact same features as the one treated here, except the consistent change of mass for all three atoms. We find very similar behaviors in the cross sections, and we confirm that the rates are faster when three identical nuclei are involved. In particular, we cannot dynamically study this system with classical trajectory methods, and we have to include properly the indistinguishability of the three (18)O nuclei; however, we note some slight differences with the (16)O(16)O(16)O benchmark system, and we focus our analysis on their origin.
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http://dx.doi.org/10.1021/acs.jpca.5b08163 | DOI Listing |
J Phys Chem A
April 2021
State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
For solving the "coordinate problem" in a product state-resolved calculation with the quantum wave packet method, an interaction-asymptotic region decomposition (IARD) method has been proposed for a general triatomic reactive scattering process. In the IARD method, the three asymptotic regions are represented by the corresponding Jacobi coordinates, but the hyperspherical coordinate is applied for representing the interaction region. For a triatomic reaction A + B with symmetry, explicit inclusion of all three channels in the calculations is unnecessary.
View Article and Find Full Text PDFJ Am Chem Soc
December 2015
Department of Chemistry and Chemical Biology, Rutgers, the State University of New Jersey, 610 Taylor Road, Piscataway, New Jersey 08854, United States.
The cobalt cubium Co4O4(OAc)4(py)4(ClO4) (1A(+)) containing the mixed valence [Co4O4](5+) core is shown by multiple spectroscopic methods to react with hydroxide (OH(-)) but not with water molecules to produce O2. The yield of reaction products is stoichiometric (>99.5%): 41A(+) + 4OH(-) → O2 + 2H2O + 41A.
View Article and Find Full Text PDFJ Phys Chem A
November 2015
Laboratoire ICB, UMR 6303, CNRS-Université de Bourgogne Franche-Comté, 21078 Dijon cedex, France.
We report rotationally resolved opacity functions, product rotational distributions, and differential cross sections for the (16)O + (16)O(16)O (v = 0,j = 1) → (16)O(16)O (v' = 0,j') + (16)O and (18)O + (18)O(18)O (v = 0,j = 1) → (18)O(18)O (v' = 0,j') + (18)O collisions calculated by a time-independent quantum mechanical method employing one of the latest potential energy surface of ozone [ Dawes ; et al. J. Chem.
View Article and Find Full Text PDFJ Phys Chem A
December 2015
Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR CNRS 6303, Université de Bourgogne Franche-Comté, 21078 Dijon Cedex, France.
We report full quantum cross sections and rate constants for the (18)O + (36)O2 → (36)O2 + (18)O collision process. This constitutes to the best of our knowledge the first dynamical study of the (18)O(18)O(18)O system, with three identical (18)O oxygen atoms. We emphasize the comparison with the (16)O + (32)O2 collision as this latter presents the exact same features as the one treated here, except the consistent change of mass for all three atoms.
View Article and Find Full Text PDFJ Chem Phys
May 2015
Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, USA.
The O + O2 isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the (18)O + (32)O2 and (16)O + (36)O2 reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES.
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