PNNL

Abstract

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The anionic and neutral complexes of glycine with water were studied at at the coupled cluster level of theory with single, double, and perturbative triple excitations. The most stable neutral complex has a relatively small dipole moment (1.74 D) and does not bind an electron. Other neutral complexes involve a polar conformer of canonical glycine and support dipole-bound anionic states. The most stable anion is characterized by an electron vertical detachment energy of 1576 cm-1, in excellent agreement with the experimental result of 1573 cm-1. The (Gly·H2O)- complex supports local minima, in which the zwitterionic glycine is stabilized by one water and one excess electron. They are, however, neither thermodynamically nor kinetically stable with respect to the dipole-bound states based on the canonical tautomers of glycine. The electron correlation contributions to excess electron binding energies are important, in particular, for nonzwitterionic complexes. Our results indicate that the condensation energies for Gly(0,-)+H2O?(Gly·H2O)(0,-) are larger than the adiabatic electron affinity of Gly·H2O. The above results imply that collisions of Gly- with H2O might effectively remove Gly- from the ion distribution. This might explain why formation of Gly- and (Gly·H2O)- is very sensitive to source conditions. We analyzed shifts in stretching mode frequencies that develop upon formation of intra- and intermolecular hydrogen bonds and an excess electron attachment. The position of the main peak and a vibrational structure in the photoelectron spectroscopy spectrum of (Gly·H2O)- are well reproduced by our theoretical results.