The public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing the burden to Department of Defense, Washington Headquarters Services Directorate for Information Operations and Reports (0704-0188), 1215 Jefferson Davis Highway, Suite 1204, Arlington VA 22202-4302. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR'S ACRONYM(S)AFRL/VSBXT SPONSOR/MONITOR'S REPORT DISTRIBUTIO NIAVAILABILITY STATEMENTApproved for public release; distribution unlimit 2 0 619 3 SUPPLEMENTARY NOTESReprinted from J. Phys. Chem., V. 110, pp. 1491-1499 © 2006, American Chemical Society. *U. of Goettingen, Goettingen, Germany #Inst. for Problems of Chem. Physics, Russian Academy of Sciences, 142432 Chernogolovka, Russia.14. ABSTRACT Statistical adiabatic channel model/classical trajectory (SACM/CT) calculations have been performed for transitional mode dynamics in the simple bond fission reactions of C 6 H 6 + -" C 6 H 5 ' + H and n-C 6 HC 4 H 9 + -C 7 H 7 + + n-C 3 H 7 . Reduced-dimensionality model potentials have been designed to take advantage ofab initio results as far as available. Average anisotropy amplitudes of the potentials were fitted by comparison of calculated specific rate constants k(EJ) with measured values. The kinetic shifts of the calculated (kU) curves and the corresponding bond energies Eo(J=O), derived as 3.90 ± 0.05 eV for C 6 H 6 + and 1.78 ± 0.05 eV for n-C 6 H 5 C 4 H 9 +, were in good agreement with literature values from thermochemical studies. Kinetic shifts from fixed tight activated complex Rice-Ramsperger-Kassel-Marcus (RRKM) theory, which also reproduces the measured k(E), were larger than the present SACM/CT results as well as earlier results from variational transition state theory (for C 6 H-6). The approach using RRKM theory was found to underestimate Eo(J=O) by about 0.2-0.3 eV. A simplified SACM/CT-based method is also proposed which circumvents the trajectory calculations and allows derivation ofEo(J=O) on the basis of measured k(E) and which provides similar accuracy as the full SACM/CT treatment. SUBJECT 0•initio results as far as available. Average anisotropy amplitudes of the potentials were fitted by comparison of calculated specific rate constants k(EJ) with measured values. The kinetic shifts of the calculated k(E) curves and the corresponding bond energies Eo(J=0), derived as 3.90 ± 0.05 eV for C 6 H 6 + and 1.78 ± 0.05 eV for n-C6HsC 4 H 9 +, were in good agreement wi...

The combination of two linear rotors forming linear or nonlinear adducts is treated using standardized valence potentials. Classical trajectory (CT) and statistical adiabatic channel (SACM) calculations are used for the calculation of thermal capture rate constants. At very low temperatures, only SACM applies. At intermediate temperatures SACM and CT approach each other; however, Landau–Zener-type multiple crossings of adiabatic channel potentials introduce local nonadiabaticity which has to be accounted for. The high-temperature transition from globally adiabatic to nonadiabatic (sudden) dynamics is studied by CT. Thermal rigidity factors, accounting for the influence of the anisotropy of the potential on the capture rate constant, are expressed in simple analytical form which facilitates practical applications. The present work complements similar studies on the addition of atoms to linear molecules in standardized valence potentials (part IV of this series).