Hydrogen-Bonded Networks in Hydride Water Clusters, F^–(H₂O)_n and Cl^–(H₂O)_n: Cubic Form of F^–(H₂O)₇ and Cl^–(H₂O)₇

Abstract

The anion-water bonds and hydrogen bonds between water molecules in X(-)(H(2)O)(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(-)(H(2)O)(7) isomers are analyzed by classifying the ligand water (L) with the numbers of the donating (n) and accepting (m) OHs as LD(n)A(m). The number of LD(0)A(2) 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 Mulliken's 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.

Electronic origin of the dependence of hydrogen bond strengths on nearest-neighbor and next-nearest-neighbor hydrogen bonds in polyhedral water clusters (H2O)n, n = 8, 20 and 24

“…In previous studies 23,34,41 , the evaluated energy is shown to be close to the counterpoise (CP) corrected HF binding energy if the augmented basis functions are used. In previous studies 23,34,41 , the evaluated energy is shown to be close to the counterpoise (CP) corrected HF binding energy if the augmented basis functions are used.…”

“…In previous studies 23,34,41 , the evaluated energy is shown to be close to the counterpoise (CP) corrected HF binding energy if the augmented basis functions are used. 41 The corresponding E apprCP_HF+MP2 /aug-cc-pVxZ binding energies are -57.6 (x=D), -61.2 (x=T), -62.1 (x=Q) and -62.5 (x=5) kJ mol −1 for Cl − (H 2 O) , 42 and -112. 41 The corresponding E apprCP_HF+MP2 /aug-cc-pVxZ binding energies are -57.6 (x=D), -61.2 (x=T), -62.1 (x=Q) and -62.5 (x=5) kJ mol −1 for Cl − (H 2 O) , 42 and -112.…”

X-ray Diffraction and Density Functional Theory Provide Insight into Vanadate Binding to Homohexameric Bromoperoxidase II and the Mechanism of Bromide Oxidation

“…72 The electronic structure model places bromide at the periphery of a octahydrate cluster 3a8, similar to minimum structures calculated for hepta-and octahydrated chloride. 73,74 The mean oxygenbromine distance in the static model of octahydrate 3a8 according to theory is 3.32 Å ( Figure 10).…”

High-Order Ca(II)–Chloro Complexes in Mixed CaCl2–LiCl Aqueous Solution: Insights from Density Functional Theory and Molecular Dynamics Simulations

“…1,4,12,13,22,[26][27][28][29][30][31][32][33][34][35][36][37][38][39][40] Generally, the hydration of anions is less of a focus than the situation of cations, although the dynamics of water molecules in the first hydration shell of anions is important in aqueous phase chemical reactions in which anions are involved 27,28,[35][36][37][38][39][40] . There are several examples of Cl − involved in simple contact ion pair/solvent-separated ion pair dynamics.…”

“…There are several examples of Cl − involved in simple contact ion pair/solvent-separated ion pair dynamics. 1,4, [11][12][13][14][15][16][17][18][19][20][21][22][23][27][28][29][30]34 In contrast to the hydration of cations, the work of Kim et al 35 and Matsuzawa et al 36 showed that the hydration of Cl − prefers surface structures. Laage and Hynes et al found the mean residence time (MRT) of water molecules around the shell of Cl − is approximately 7−11 ps, supporting a labile, nonrigid Cl − hydration shell.…”