Low-energy structures of hydrated hydride ions .
Low-temperature favorable and room-temperature entropy-driven structures of hydrated hydride anions.
interaction energy components of the mono-hydrated hydride ion.
Potential energy surface (PES) of the proton transfer from water to hydride ion at the , , and levels.
Ground and excited states of the hexahydrated hydride tweezers. The excited state would reflect the virtual orbital of the hydride ion.
DFT-MD simulations of and at . The geometrical structures at the beginning and at the end of the simulations are shown. The subscripts and denote the H-acceptor and donor water molecules, respectively.
Excited-state AIMD simulations of at . The distance between the hydride ion and the nearest O atom in the water cluster (Å) (a), evolution of kinetic energies (kcal/mol) (b), NBO charges of the hydride ion (c), potential energy surface (d) along the excited-state MD trajectory (e). The detachment of the hydrogen radical is clearly seen.
IR spectra for the OH stretches of the hydrated hydride ion clusters (scale factor: 0.96). The second figure of IR spectra was of monohydrated hydride from the CPMD calculation at (scale factor; 1.025).
Hydration energies of hydrated hydride anions. (Interaction energies were corrected by 50% BSSEs by which the lower and upper limit is the BSSE corrected and uncorrected values, respectively. The B3LYP thermal energies were used in all results.)
Geometric parameters and electronic properties of the hydride anion and hydrated hydride anions. (cn/hb is the number of coordination of the hydride ion/the number of the water-water H bonds. is the average distance between the hydride anion and the oxygen atoms of primary water molecules. The charge of hydrated hydride ion is the natural bond orbital (NBO) charge (and Mulliken charge in brackets). is the HOMO-LUMO energy gap at the level. is the dipole moment of the geometry at the neutral state. is the polarizability vector at the level. VDE is vertical-electron detachment energy in eV at the level. and are the CTTS energies (in nm) at the CIS and levels. are the vertically and adiabatically transferred NBO charges of the hydrated hydride anions via the CTTS process at the level. is the shortest distance (in Å) between the hydride ion and the oxygen atom of water at the vertically excited state, plus the increased distance for the optimized CTTS state at the level.)
scaled frequencies ( and in ) and IR intensities (in in parentheses) for the OH stretching and bending modes of hydrated hydride ions, . The frequencies were scaled by 0.96 to match the average value of asymmetric and symmetric stretch frequencies of with the corresponding experimental value (Ref. 29). Superscripts I, W, and D indicate the OH stretches of ion-water interaction, water-water H-bond interaction, and free dangling H, respectively. Subscripts a, da, dda, and d denote a-, da-, dda-, and d-type water molecules, where a and d mean the H acceptor and donor, respectively.
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