A theoretical study of the photodetachment and intramolecular hydrogen-bonding energies of hydrogen maleate anions

Three low-lying conformers of the hydrogen maleate anions (HMAs) regarding cis-HMA(HB) having the O-center dot center dot center dot HO intramolecular hydrogen bond (HB), cis-HMA(nHB) without the HB, and trans-HMA are studied by density functional theory (B3LYP) combined with natural bond orbital (NBO) and atoms-in-molecules (AIM) analyses. The photoelectron spectra of cis- and trans-HMA conformers recorded by Woo et al. (J. Phys. Chem. A 2005, 109, 10633) are reassigned on the basis of the present electron propagator theory calculations, indicating the significant energy differences between the Dyson orbitals and canonical molecular orbitals due to the electron-correlation and orbital relaxation effects considered in the electron propagator theory. The NBO associated with the natural resonance theory analyses and AIM electron topological study show that the strong O-center dot center dot center dot HO in cis-HMA(HB) has the remarkable characteristics of three-center four-electron hyperbond, and the bonding strength of ca. 30 kcal/mol is recommended with the reference calculations of the HO-center dot center dot center dot HOH complex. The further calculations for the microhydrated cis-HMA(HB) clusters indicate that the O-center dot center dot center dot HO bonding strength decreases in water solution.