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J Chem Phys. 2012 Oct 7;137(13):134306. doi: 10.1063/1.4757150.

Thermochemical analysis and kinetics aspects for a chemical model for camphene ozonolysis.

Author information

1
Departamento de Química, Universidade Federal Rural do Rio de Janeiro, Rodovia BR465, Km 7, Seropédica, RJ 23890-000, Brazil.

Abstract

In this work, a chemical model for the camphene ozonolysis, leading to carbonyl final products, is proposed and discussed on the basis of the thermochemical properties and kinetic data obtained at density functional theory levels of calculation. The mechanism is initiated by the electrophilic attack of ozone to the double bond in camphene leading to a 1,2,3-trioxolane intermediate, which decomposes to peroxy radicals and carbonyl compounds in a total of 10 elementary reactions. The thermodynamic properties (enthalpy and entropies differences) are calculated at 298 K. For the thermochemical evaluation, theoretical calculations are performed with the B3LYP, MPW1PW91, and mPW1K density functionals and the basis sets 6-31G(d), 6-31G(2d,2p), 6-31+G(d,p), and 6-31+G(2d,2p). Eventually, single point calculations adopting the 6-311++G(2d,2p) basis set are performed in order to improve the electronic energies. The enthalpy profiles suggest highly exothermic reactions for the individual steps, with a global enthalpy difference of -179.18 kcal mol(-1), determined at the B3LYP∕6-31+G(2d,2p) level. The Gibbs free energy differences for each step, at 298 K, calculated at the B3LYP∕6-311++G(2d,2p)∕∕B3LYP∕6-31+G(2d,2p) level, are used to estimate the composition of a final product mixture under equilibrium conditions as 58% of camphenilone and 42% of 6,6-dimethyl-ɛ-caprolactone-2,5-methylene. For the reaction kinetics, the bimolecular O(3) + camphene step is assumed to be rate determining in the global mechanism. A saddle point for the ozone addition to the double bond is located and rate constants are determined on the basis of the transition state theory. This saddle point is well represented by a loosely bound structure and corrections for the basis set superposition error (BSSE) are calculated, either by considering the effect over the geometry optimization procedure (here referred as CP1 procedure), or the effect of the BSSE over the electronic energy of a previously optimized geometry, included a posteriori (here referred as CP2). The rate constants, calculated at 298 K from the data obtained at the mPW1K∕6-31+G(d,p), CP1∕B3LYP∕∕6-31+G(2d,2p), and CP2∕B3LYP∕∕6-31+G(2d,2p) levels (3.62 × 10(-18), 1.12 × 10(-18), and 1.39 × 10(-18) cm(3) molecule(-1) s(-1)), are found in good agreement with the available experimental data at the same temperature, 0.9 × 10(-18) cm(3) molecule(-1) s(-1) [R. Atkinson, S. M. Aschmann, and J. Arey, Atmos. Environ. 24, 2647 (1990)]. The importance of the BSSE corrections for the final rate constants must be pointed out. Furthermore, this work will contribute to a better understanding of the chemistry of monoterpenes in the atmosphere, as well as the implications for the phenomena of pollution.

PMID:
23039598
DOI:
10.1063/1.4757150
[Indexed for MEDLINE]

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