Theoretical studies of structures and ionization threshold energies of water cluster complexes with a group 1 metal, M(H2O)(n) (M = Li and Na)

Citation
T. Tsurusawa et S. Iwata, Theoretical studies of structures and ionization threshold energies of water cluster complexes with a group 1 metal, M(H2O)(n) (M = Li and Na), J PHYS CH A, 103(31), 1999, pp. 6134-6141
Citations number
17
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
10895639 → ACNP
Volume
103
Issue
31
Year of publication
1999
Pages
6134 - 6141
Database
ISI
SICI code
1089-5639(19990805)103:31<6134:TSOSAI>2.0.ZU;2-W
Abstract
Water cluster complexes with a group 1 metal atom, M(H2O), (M = Li and Na), for n = 3-6 were studied with ab initio MO methods. The singly occupied mo lecular orbitals (SOMOs) are classified into three types: surface, quasi-va lence, and semi-internal. It is the isomers of structures with semiinternal SOMO that are responsible for the observed convergence of the ionization t hreshold energy. They are the ion-pair complexes, M+(H2O)(m).(H2O)(l).(H2O) (n-m-l)(-), and their vertical ionization energies (VIEs) are determined by the local structure of (H2O)(n-m-l)(-), and the electrostatic potential fr om the cation M+(H2O)(m). The model also explains why the experimental ioni zation threshold energy converges at n = 4.