TY - JOUR
T1 - Hydrogen-Bonded Networks in Hydride Water Clusters, F-(H2O)n and Cl-(H2O)n
T2 - Cubic Form of F-(H2O)7 and Cl-(H2O)7
AU - Ishibashi, Chiaki
AU - Iwata, Suehiro
AU - Onoe, Kaoru
AU - Matsuzawa, Hidenori
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/10/8
Y1 - 2015/10/8
N2 - The anion-water bonds and hydrogen bonds between water molecules in X-(H2O)n (X = F and Cl, n = 3-7) clusters are analyzed by evaluating the charge-transfer (CT) and dispersion terms for every pair of ions and molecules with the perturbation theory based on the locally projected molecular orbitals. In particular, the relative stabilities and the bond strengths in all 11 distinct cubic X-(H2O)7 isomers are analyzed by classifying the ligand water (L) with the numbers of the donating (n) and accepting (m) OHs as LDnAm. The number of LD0A2 waters determines the relative stability. It is demonstrated that the strengths of the anion-ligand bonds are strongly influenced by two other hydrogen bonds of the water molecules adjacent to the ligand. When the model theory of Mullikens charge-transfer interaction is applied to the anion-ligand and water-water hydrogen bonds, the dependence of the bond strengths on the chains of the hydrogen bonds is explained.
AB - The anion-water bonds and hydrogen bonds between water molecules in X-(H2O)n (X = F and Cl, n = 3-7) clusters are analyzed by evaluating the charge-transfer (CT) and dispersion terms for every pair of ions and molecules with the perturbation theory based on the locally projected molecular orbitals. In particular, the relative stabilities and the bond strengths in all 11 distinct cubic X-(H2O)7 isomers are analyzed by classifying the ligand water (L) with the numbers of the donating (n) and accepting (m) OHs as LDnAm. The number of LD0A2 waters determines the relative stability. It is demonstrated that the strengths of the anion-ligand bonds are strongly influenced by two other hydrogen bonds of the water molecules adjacent to the ligand. When the model theory of Mullikens charge-transfer interaction is applied to the anion-ligand and water-water hydrogen bonds, the dependence of the bond strengths on the chains of the hydrogen bonds is explained.
UR - http://www.scopus.com/inward/record.url?scp=84943602217&partnerID=8YFLogxK
U2 - 10.1021/acs.jpca.5b07244
DO - 10.1021/acs.jpca.5b07244
M3 - Article
AN - SCOPUS:84943602217
SN - 1089-5639
VL - 119
SP - 10241
EP - 10253
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 40
ER -