Local control theory double well potentials

Studies of proton transfers involving small ions with localized charge have shown that these reactions may proceed indeed with rate constants close to or even slightly larger than the collision rate constants predicted by the ADO theory (Mackay et al., 1976). However, rate-constant measurements of proton-transfer reactions between delocalized anions (Farneth and Brau-man, 1976) and sterically hindered pyridine bases (Jasinski and Brauman, 1980) and of SN2 displacement reactions (Olmstead and Brauman, 1977 Pellerite and Brauman, 1980 Pellerite and Brauman, 1983 Caldwell et al., 1984 for a review see Riveros et al., 1985) have shown that the rate constants can span the range from almost collision controlled values down to ones too slow to be observed. For these reactions the wide variation in rate constants has been explained on the basis of a double potential-well model which for a hypothetical SN2 substitution is schematically shown in Fig. 4. 

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See also in sourсe #XX -- [ , , , , , ]

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