CHARACTERIZATION OF LOW-BARRIER HYDROGEN-BONDS .1. MICROSOLVATION EFFECTS - AN AB-INITIO AND DFT INVESTIGATION

Hartree-Fock, Moller-Plesset, and DFT calculations have been carried o ut using the 6-31++G* basis set to study the effect of microsolvation on the strength of a typical low-barrier hydrogen bond. In the gas ph ase, the hydrogen bond formed between a formic acid molecule and a for mate anion is approximately 25 kcal/mol, with a calculated energy barr ier for proton transfer from the formic acid to the formate anion whic h is lower than the zero point vibrational energy resonant in the syst em. When both the formic acid and formate anion are microsolvated, by one water molecule each, the resulting hydrogen bond is actually incre ased in strength slightly. When the microsolvation is asymmetrical, ho wever, so as to cause a mismatch in the pK(a) values of the hydrogen b ond donor and hydrogen bond acceptor, the resulting H-bond is weakened by approximately 4 kcal/mol. These results suggest that small amounts of interstitial water in enzyme active sites may not preclude the exi stence or importance of low-barrier hydrogen bonds in such biological catalysts.