On the transition-state region of the O(3P) + O2(3Σg-) potential energy surface

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 O2 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+O2 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+O2→O3* capture cross section and rate constant when the new potential energy surface is employed are investigated by means of classical trajectory calculations.

[1]  M. Joyeux,et al.  Semiclassical dynamics of the van der Waals states in O3(X1A1). , 2004, The Journal of chemical physics.

[2]  K. Morokuma,et al.  New ab initio potential surfaces and three-dimensional quantum dynamics for transition state spectroscopy in ozone photodissociation , 1992 .

[3]  Jensen,et al.  Determination of the Effective Ground State Potential Energy Function of Ozone from High-Resolution Infrared Spectra. , 1999, Journal of molecular spectroscopy.

[4]  S. Peyerimhoff,et al.  Potential energy surfaces of ozone in its ground state and in the lowest-lying eight excited states , 1993 .

[5]  R. T. Pack,et al.  Does ozone have a barrier to dissociation and recombination , 2002 .

[6]  Martina Bittererová,et al.  Spectroscopy of ozone at the dissociation threshold : Quantum calculations of bound and resonance states on a new global potential energy surface , 2001 .

[7]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[8]  M. Wiegell,et al.  The temperature dependence of the exchange reaction between oxygen atoms and dioxygen molecules studied by means of isotopes and spectroscopy , 1997 .

[9]  Robert B. Walker,et al.  Metastable states of ozone calculated on an accurate potential energy surface , 2003 .

[10]  Hua Guo,et al.  Accurate ab initio near-equilibrium potential energy and dipole moment functions of the ground electronic state of ozone , 2000 .

[11]  Robert B. Walker,et al.  Formation of ozone: Metastable states and anomalous isotope effect , 2003 .

[12]  P. Rosmus,et al.  The asymptotic region of the potential energy surfaces relevant for the O(3P)+O2(X3Σg-) ⇋ O3 reaction , 2002 .

[13]  P. Fleurat‐Lessard,et al.  Isotope dependence of the O+O2 exchange reaction: Experiment and theory , 2003 .

[14]  T. Dunning,et al.  A Road Map for the Calculation of Molecular Binding Energies , 2000 .

[15]  Paul Fleurat-Lessard,et al.  van der Waals states in ozone and their influence on the threshold spectrum of O3(X1A1). I. Bound states. , 2003 .

[16]  R. Schinke,et al.  The effect of spin-orbit coupling in complex forming O(3P) + O2 collisions , 2003 .

[17]  J. Light,et al.  Vibrational energy levels of ozone up to dissociation revisited. , 2004, The Journal of chemical physics.

[18]  Kenneth R. Hall,et al.  Thermodynamic Properties of Key Organic Oxygen Compounds in the Carbon Range C1 to C4. Part 1. Properties of Condensed Phases , 1985 .

[19]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure: I. Spectra of Diatomic Molecules , 1944 .

[20]  Robert J. Harrison,et al.  A SYSTEMATIC AB INITIO INVESTIGATION OF THE OPEN AND RING STRUCTURES OF OZONE , 1998 .

[21]  F. S. Klein,et al.  Kinetics of the isotope exchange reaction of 18O with NO and O2 at 298 K , 1985 .

[22]  P. Fleurat‐Lessard,et al.  The vibrational energies of ozone up to the dissociation threshold: Dynamics calculations on an accurate potential energy surface , 2002 .

[23]  P. Fleurat‐Lessard,et al.  Theoretical investigation of the temperature dependence of the O+O2 exchange reaction , 2003 .

[24]  Trygve Helgaker,et al.  Basis-set convergence in correlated calculations on Ne, N2, and H2O , 1998 .

[25]  Rodney J. Bartlett,et al.  Approximately extensive modifications of the multireference configuration interaction method: A theoretical and practical analysis , 1995 .