TY - JOUR
T1 - Mechanism of hydroxide mobility
AU - Agmon, Noam
PY - 2000/3/17
Y1 - 2000/3/17
N2 - A suggested mechanism for hydroxide mobility in water identifies the rate limiting step as a cleavage of a second shell hydrogen bond which converts a H7O4- ion (triply coordinated hydroxide) to (HOHOH)- (deprotonated water dimer). Proton transfer is enabled by an additional O-O bond contraction, not required in H5O2+. This explains why the activation energy for hydroxide mobility is larger than that of proton mobility by about 0.5 kcal/mol. The transfer cycle is terminated by hydrogen-bond formation to the other oxygen center. Available experimental data, and most of the computational results, can be rationalized in the framework of the above model.
AB - A suggested mechanism for hydroxide mobility in water identifies the rate limiting step as a cleavage of a second shell hydrogen bond which converts a H7O4- ion (triply coordinated hydroxide) to (HOHOH)- (deprotonated water dimer). Proton transfer is enabled by an additional O-O bond contraction, not required in H5O2+. This explains why the activation energy for hydroxide mobility is larger than that of proton mobility by about 0.5 kcal/mol. The transfer cycle is terminated by hydrogen-bond formation to the other oxygen center. Available experimental data, and most of the computational results, can be rationalized in the framework of the above model.
UR - http://www.scopus.com/inward/record.url?scp=0001537164&partnerID=8YFLogxK
U2 - 10.1016/S0009-2614(00)00136-6
DO - 10.1016/S0009-2614(00)00136-6
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AN - SCOPUS:0001537164
SN - 0009-2614
VL - 319
SP - 247
EP - 252
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 3-4
ER -