Journal of Physical Chemistry A, Vol.103, No.33, 6632-6637, 1999
The role of a short and strong hydrogen bond on the double proton transfer in the formamidine-formic acid complex: Theoretical studies in the gas phase and in solution
Multiproton transfer in which more than one proton is transferred, either synchronously or asynchronously, is an important phenomenon in chemistry and biology. The hydrogen bonds with a very low barrier, leading to proton delocalization in the H-bond, are called "short strong" or "low-barrier" hydrogen bonds (SSHB or LBHB). It has recently been proposed that they may provide an unusually large amount of stabilization to high-energy enzyme-bound intermediates and/or transition states. In order to study the role of such hydrogen bonds in the multiproton transfer, we have performed high-level ab initio quantum mechanical calculations for the potential energy surface of the formamidine-formic acid complex. The double-proton transfer occurs asynchronously with a strongly hydrogen bonded intermediate, and the barrier height is 3.95 kcal mol(-1), which is about 5-12 kcal mol(-1) lower than those of the concerted reactions in formamidine dimer and in formic acid dimer. The SSHB changes not only the barrier height but also the mechanism of the double-proton transfer. The strength of SSHB depends on environments. We have calculated the solvent effect at the HF and the B3LYP levels using the self-consistent isodensity polarized continuum model (SCIPCM). The strength of SSHB is reduced rapidly with increasing dielectric constants. It is about 29 kcal mol(-1) at epsilon = 10. The barrier height is also reduced with increasing dielectric constants, which indicates that the proton transfer becomes faster in a polar medium. These results suggest that the SSHB contribute to the proton transfer,greatly, and the energetics is changed very much with environment.