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In Tables I and II A stands for atom, L for linear molecule, and N for nonlinear molecule. Any ionic fragment should be treated as an atom.47 The quadrupole tensor of the fragment is assumed to have the form of Eq. (67d)
-
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45
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21444442248
-
-
note
-
The hypothetical system in which the potential can be represented by Eq. s32d while Eq. s9d is not satisfied, may consist of one very light fragment, e.g., the hydrogen atom or ion, and a very heavy one, with large inertia moments. The chemical interaction in such a system should be weak and the long-range interaction should be strong.
-
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47
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21444439471
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note
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If the higher order terms in the potential expansion, Eq. (31) are neglected for reactions in which one of the fragments is ionic, only the rotational degrees of freedom of the nonionic fragment should be considered, because the rotational degrees of freedom of the ionic fragment are then totally uncoupled from the reaction dynamics. It is then best to simply neglect these degrees of freedom in the calculation of the rate constant.
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50
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Reference, p. 963
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Reference, p. 963.
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51
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21444458049
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note
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The conclusion made in Ref. 28 strongly influenced subsequent theoretical development, see, e.g., Refs. 13, 62, and 67.
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58
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21444456196
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note
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The interfragment interaction potential effectively depends on the isotopic composition of the fragments due to the isotopic displacement of the fragments' centers of mass. We assume here that the effect of this dependence on the rate constant is negligible.
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60
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0000955345
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The only exception we are aware about is Ref. 36, where it was shown that taking into account the conservation of the angular momentum for the ion-linear dipole reactive system explains the differences with the trajectory simulation.
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63
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21444450853
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note
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Equations s2.7d, s2.4d, and s2.5d in Refs. 53, 68, and 55, correspondingly.
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68
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