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Silver as an electron source for photodissociation of hydronium
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10.1063/1.3659702
/content/aip/journal/jcp/135/20/10.1063/1.3659702
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/20/10.1063/1.3659702

Figures

Image of FIG. 1.
FIG. 1.

Silver cluster. Distance between layers expanded for clarity. See text for details.

Image of FIG. 2.
FIG. 2.

Optimized solvated hydronium geometry. Lighter colored atoms are considered part of the CI-active space, and were allowed greater geometric flexibility during optimization.

Image of FIG. 3.
FIG. 3.

Depiction of parameters for geometric optimizations. (a) Stretching of initial O–H bond; (b) approach of hydrogen to oxygen of neighboring water; (c) dissociation of hydrogen from system; and (d) dissociation of H2 from system.

Image of FIG. 4.
FIG. 4.

Singly occupied molecular orbitals for the constrained triplet at the starting geometry. Left panel contours: ±0.005; Right panel contours: ±0.025.

Image of FIG. 5.
FIG. 5.

Potential curves for the first three states of the hydrogen transfer and dissociation reaction. The numerical value of the OH distance (Å) is given for each point using definitions in Fig. 3. Region A: transition from ground-state minimum energy geometry to the transition state for hydrogen transfer via the excited state. Region B: transition from transition state to a geometry where hydrogen has been fully transferred. Region C: removal of hydrogen atom.

Image of FIG. 6.
FIG. 6.

Initial hydrogens-up geometry.

Image of FIG. 7.
FIG. 7.

Potential curves for the first three states during hydrogen transfer starting from a hydrogens-up geometry. The numerical value of the OH distance (Å) is given for each point using definitions in Fig. 3. Region A: transition from the ground state minimum energy geometry to the transition state for hydrogen transfer via the excited state. Region B: transition from the transition state to a geometry where hydrogen has been fully transferred. Region C: removal of hydrogen atom.

Image of FIG. 8.
FIG. 8.

Typical intermediate geometry for H2.

Image of FIG. 9.
FIG. 9.

Potential curves for the first three states of the hydrogen transfer and H2 formation reaction. The numerical value of the OH/HH distance (Å) is given for each point using definitions in Fig. 3. Region A: transition from the ground state minimum energy geometry to the transition state for hydrogen transfer via the excited state. Region B: transition from the transition state to a geometry where hydrogen has been fully transferred. Region C: removal of hydrogen molecule.

Image of FIG. 10.
FIG. 10.

Combined potential curves for all studied reactions. Blue (dark) curves represent the reaction which a hydrogens-down initial orientation for the hydronium, while yellow (light) curves the hydrogens-up reaction. Circles indicate H2O + H product pathways, while diamonds indicate OH + H2 product pathways. Solid curves are the energies of the electron transfer excited state, while dashed curves are the ground state.

Tables

Generic image for table
Table I.

Thermodynamic estimates.

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/content/aip/journal/jcp/135/20/10.1063/1.3659702
2011-11-22
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Silver as an electron source for photodissociation of hydronium
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/20/10.1063/1.3659702
10.1063/1.3659702
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