Rm. Minyaev, BIPROTON TRANSFER IN ASSOCIATES OF THE FORMIC-ACID MOLECULE WITH H2O-CENTER-DOT-CENTER-DOT-CENTER-DOT-YH SYSTEMS (YH=H2O,HOF AND HOOH), Journal of structural chemistry, 37(5), 1996, pp. 713-721
An ab initio (STO-3G basis set) method is used to calculate the pathwa
ys and activation barriers of cooperative biproton migrations in the a
ssociates of the formic acid molecule with water and YH (YH=H2O, HOF,
and HOOH). The associate with YH = H2O exhibits a cooperative triproto
n transfer with an activation barrier of 4.46 (C-s symmetry) or 3.08 k
cal/mole (C-2 symmetry); in the systems with Y = HOF and HOOH, the bip
roton transfer is accompanied by synchronous shifts of two hydroxyl gr
oups and has the activation barriers of 75.03 (C-2, Y = HOF) 75.74 (C-
s, Y = HOF) and 89.62 kcal/mole (Y = HOOH). The hypothesis of stereoch
emical similarity for low-barrier cooperative processes in molecular a
ssociates is proposed.