Article

# The transition-state region of the O((3)P)+O(2)((3)Sigma(g) (-)) potential energy surface.

Max-Planck-Institut für Strömungsforschung, Bunsenstrasse 10, D-37073 Göttingen, Federal Republic of Germany.

The Journal of Chemical Physics (Impact Factor: 2.95). 09/2004; 121(12):5789-93. DOI: 10.1063/1.1784776 Source: PubMed

**ABSTRACT**

New electronic structure calculations for the transition-state region of the lowest ozone potential energy surface are reported. A two-dimensional potential energy surface in the asymptotic channel is calculated with the O(2) bond distance being fixed. The calculations are performed at the multireference average quadratic coupled cluster level of theory using full-valence complete active space self-consistent field wave functions and the augmented correlation consistent polarized V6Z atomic basis set. The general shape of the potential energy surface as predicted in earlier studies, that is, a narrow transition state below the O+O(2) asymptote, is confirmed by the present calculations. The transition state is 181 cm(-1) below the asymptote and 72 cm(-1) above the van der Waals-like minimum. The changes in the O+O(2)-->O(3) (*) capture cross section and rate constant when the new potential energy surface is employed are investigated by means of classical trajectory calculations.

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**ABSTRACT:**The effect of zero-point energy differences (DeltaZPE) between the possible fragmentation channels of highly excited O(3) complexes on the isotope dependence of the formation of ozone is investigated by means of classical trajectory calculations and a strong-collision model. DeltaZPE is incorporated in the calculations in a phenomenological way by adjusting the potential energy surface in the product channels so that the correct exothermicities and endothermicities are matched. The model contains two parameters, the frequency of stabilizing collisions omega and an energy dependent parameter Delta(damp), which favors the lower energies in the Maxwell-Boltzmann distribution. The stabilization frequency is used to adjust the pressure dependence of the absolute formation rate while Delta(damp) is utilized to control its isotope dependence. The calculations for several isotope combinations of oxygen atoms show a clear dependence of relative formation rates on DeltaZPE. The results are similar to those of Gao and Marcus [J. Chem. Phys. 116, 137 (2002)] obtained within a statistical model. In particular, like in the statistical approach an ad hoc parameter eta approximately 1.14, which effectively reduces the formation rates of the symmetric ABA ozone molecules, has to be introduced in order to obtain good agreement with the measured relative rates of Janssen et al. [Phys. Chem. Chem. Phys. 3, 4718 (2001)]. The temperature dependence of the recombination rate is also addressed.The Journal of Chemical Physics 04/2005; 122(9):094317. DOI:10.1063/1.1860011 · 2.95 Impact Factor - [Show abstract] [Hide abstract]

**ABSTRACT:**Three-dimensional diabatic potential energy surfaces for the lowest four electronic states of ozone with 1A' symmetry-termed X, A, B, and R-are constructed from electronic structure calculations. The diabatization is performed by reassigning corresponding energy points. Although approximate, these diabatic potential energy surfaces allow one to study the uv photodissociation of ozone on a level of theory not possible before. In the present work photoexcitation in the Hartley band and subsequent dissociation into the singlet channel, O3X+hnu-->O(1D)+O2(a 1Deltag), are investigated by means of quantum mechanical and classical trajectory calculations using the diabatic potential energy surface of the B state. The calculated low-resolution absorption spectrum as well as the vibrational and rotational state distributions of O2(a 1Deltag) are in good agreement with available experimental results.The Journal of Chemical Physics 09/2005; 123(7):074305. DOI:10.1063/1.2001650 · 2.95 Impact Factor - [Show abstract] [Hide abstract]

**ABSTRACT:**It is shown that standard computations of electronic structures of polyatomic systems that yield the global minimum configuration and vibrational frequencies may be faulty if the symmetry of this configuration is lower than the highest possible one and the origin of this distortion, which is always due to the Jahn-Teller effect, is neglected; this may lead, in particular, to the loss of the Berry phase factor that changes the vibronic energy level spectrum and which we show to be present even when there are no apparent conical intersections. The general case and the ozone molecule are analyzed.Physical Review Letters 05/2006; 96(16):163005. DOI:10.1103/PhysRevLett.96.163005 · 7.51 Impact Factor

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