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- W1991087210 abstract "The ter-molecular association processes involving CH+3 or a deuterated analog as the ionic reactant, H2, HD, or D2 as the neutral reactant and CH+5, CH4D+, CH3D+2, CH2D+3, CHD+4, and CH+5 as the product are investigated theoretically. Going from process to process along the sequence there are increases in the energy density of vibrational states, changes in the symmetry numbers of the reactants and of the products and changes also in the number of distinguishable isomeric products. Furthermore in the low temperature region H2 is markedly less efficient than HD or D2 as an association partner. Taking these effects into account it is found that the ter-molecular association coefficients at 80 K rise irregularly in going along the sequence from CH+5 to CH2D+3 (by a total factor of about 27) and then fall irregularly in continuing on to CD+5 (by a further total factor of 3.7). This is in apparent serious conflict with laboratory measurements in ambient helium which show much less variation along the sequence (with the values of the two factors just specified only 5.6 and 1.6, respectively). It is shown that the pressure of the ambient helium (0.4 Torr) was much too high for the third order kinetics that were implicitly assumed to prevail, even for the slowest process (CH+5 association) the ambient helium pressure would have had to be at least around ten times smaller to avoid the measured rate coefficient at 80 K being around 20% or more less than its low ambient gas density limit. The necessary corrections are made. They bring about excellent agreement between theory and experiment. The study yields a value for the CH+5 vibrational density of states." @default.
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- W1991087210 date "1986-09-01" @default.
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- W1991087210 title "Some ter‐molecular association processes in collisions of CH+3and its deuterated analogs with H2, HD, and D2" @default.
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- W1991087210 doi "https://doi.org/10.1063/1.451071" @default.
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