Structures, energetics, and spectra of electron–water clusters, e−–(H2O)2–6 and e−–HOD(D2O)1–5

Abstract

Although various low-lying energy structures of electron–water clusters, e−–(H2O)2–6, have been reported, some of the global minimum energy structures (in particular, for the tetramer and pentamer) are still not clearly characterized yet. Therefore, using high-level ab initio calculations, we have investigated several new low-lying energy conformers in addition to previously reported ones. The lowest energy conformer for the pentamer is found to have a wedge-like structure which has never been studied before. Based on the experimental vertical electron-detachment energies and OH vibrational spectra of the electron–water clusters, we report the most probable structures and their nearly isoenergetic structures. The OH vibrational frequencies of e−(H2O)2–6 and e−HOD(D2O)1–5 are investigated, and are found to be in excellent agreement with the available experimental data. Their O–H stretch frequency shifts are classified in terms of the types of water molecules.