Characterization of low-barrier hydrogen bonds .3. Hydrogen maleate. An ab initio and DFT investigation

High-level ab initio molecular orbital and density functional theory calculations predict the existence of a very short-strong hydrogen bond in the monoanion of maleic acid (hydrogen maleate). At all levels of theory (HF, MP2, BLYP, and B3LYP) except B3PW91 the potential energy surface is predicted to contain two minima, and hence resembles a double well. The barrier to proton transfer via a symmetrical transition state is calculated to be very small at all levels of theory. In all cases the calculated zero point vibrational energy available to the system is larger than the calculated barrier for proton transfer, thus the resulting hydrogen bond formed in hydrogen maleate is predicted to be symmetrical. Using the B3PW91 functional and the 6-31+G(d,p) basis set results in a single-well potential and a symmetrically positioned hydrogen. All correlated methods predict the gas phase hydrogen bond energy to be approximately 27 kcal/mol. Effects due to solvents were estimated using solvent cavity methods. Approximating the solvent as a dielectric continuum reduces the calculated hydrogen bond energy by roughly 6 kcal/mol at all levels of theory.