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).
The addition of atoms to linear molecules forming linear or nonlinear adducts is treated using standardized valence potentials. The dynamics is analyzed with a combination of classical trajectory (CT) and statistical adiabatic channel (SACM) calculations. For classical adiabatic conditions, the two approaches coincide. The transition from adiabatic to nonadiabatic dynamics is investigated using CT calculations. The low-temperature adiabatic quantum range is studied by SACM. Thermal capture rate constants are represented in analytical form. Thermal rigidity factors are expressed in terms of molecular parameters such as the frequencies of transitional bending modes, the bond dissociation energy, the rotational constant of the linear fragment, and the ratio of the looseness and Morse parameters α/β of the potential-energy surface. The final rate expressions are of simple form suitable for direct practical applications.
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