Journal of Chemical Physics, Vol.108, No.18, 7670-7678, 1998
Temperature dependence and dynamical instability in the Hartley absorption system of ozone
Analysis of weak oscillations in the Hartley absorption system of ozone via the equivalent recurrences in the autocorrelation function is found to reveal a clear temperature effect. Previous classical trajectory studies of unstable nearly periodic orbits associated with these oscillations/ recurrences are extended to examine the possibility that strong sensitivity to initial rotational conditions is responsible. Using minimum return distance in phase space as an expedient measure for the stability of the orbits, evidence is found for particular destabilization due to in-plane rotations of the ozone molecule. A model for the recurrence temperature dependence is constructed based on this mechanism, and the implications for comparison of theoretical and experimental recurrence intensities are discussed.
Keywords:ANHARMONIC POTENTIAL FUNCTION;PERIODIC-ORBITS;POLYATOMIC-MOLECULES;SYMMETRIC TRIATOMICS;PHOTO-DISSOCIATION;ENERGY SURFACES;CROSS-SECTION;HYDROGEN-ATOM;PHOTODISSOCIATION;SPECTRA