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The static-exchange electron-water pseudopotential, in conjunction with a polarizable water model: A new Hamiltonian for hydrated-electron simulations
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10.1063/1.3089425
/content/aip/journal/jcp/130/12/10.1063/1.3089425
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/12/10.1063/1.3089425

Figures

Image of FIG. 1.
FIG. 1.

Comparison of VEBEs obtained with various ab initio methods to those obtained at the CCSD(T) level, for a set of 24 cluster isomers ranging from to , each of which is a stationary point at the level. The MP2 and CCSD(T) calculations employ the basis set, while the density-functional calculations use the basis. LRC-BOP calculations employ a range-separation parameter of , as recommended in Ref. 76. The diagonal line indicates where the predicted VEBE is the same as the CCSD(T) value.

Image of FIG. 2.
FIG. 2.

Comparison of VEBEs computed at the level of theory to those predicted using model Hamiltonians, for (a) 32 isomers ranging from to , and (b) 59 isomers ranging from to . The diagonal line indicates where the model Hamiltonian and MP2 predications are identical.

Image of FIG. 3.
FIG. 3.

Comparison of VEBEs computed at the level of theory to those predicted using model Hamiltonians, for isomers (with ) that were (a) extracted from a MD simulation, as described in the text; and (b) subsequently optimized, using the TB model.

Image of FIG. 4.
FIG. 4.

Structures of the , , and isomers used to benchmark relative conformational energies. Each geometry shown here is a stationary point at the level.

Image of FIG. 5.
FIG. 5.

Energies of tetrameric clusters on (a) the potential surface and (b) the potential surface. Note that the two panels use different energy scales. Ab initio geometries for each cluster are depicted in Fig. 4.

Image of FIG. 6.
FIG. 6.

Energies of pentameric clusters on (a) the potential surface and (b) the potential surface. Note that the two panels use different energy scales. Ab initio geometries for each cluster are depicted in Fig. 4.

Image of FIG. 7.
FIG. 7.

Stationary points of isomers on the TB potential surface compared to stationary points at the level.

Image of FIG. 8.
FIG. 8.

Energies of hexameric clusters on (a) the potential surface and (b) the potential surface. Note that the two panels use different energy scales. Ab initio geometries for each cluster are depicted in Fig. 4. Isomer hex2 is omitted, for reasons discussed in the text.

Image of FIG. 9.
FIG. 9.

Comparison of the TB model (dashed curves) and the new potential (solid curves) for , in four one-dimensional slices. To facilitate the comparison, both potentials are shown without polarization. In (a)–(c), represents the center of mass, whereas in (d), at the oxygen atom.

Image of FIG. 10.
FIG. 10.

Plots of the pseudopotential for using various -type exchange potentials of the form , where is defined in Eq. (38). Values of the scaling parameter range from (the top curve, in red, which is least attractive) to (the bottom curve, in black, which is most attractive), in increments of 0.2. In (a)–(c), represents the center of mass, whereas in (d), at the oxygen atom.

Image of FIG. 11.
FIG. 11.

Histograms of the average repulsion energy, for a library of isomers.

Image of FIG. 12.
FIG. 12.

Histograms illustrating the change in the polarization energy of the water molecules when an electron is added to a water cluster assembled in its anion geometry, as defined in Eq. (39). Expectation values are binned over a library of isomers. Results are shown only for the polarizable model.

Image of FIG. 13.
FIG. 13.

Histogram of the total polarization energy, as defined in Eq. (41), binned over a library of isomers. Results are shown only for the polarizable model developed here.

Image of FIG. 14.
FIG. 14.

Histogram of the electron-water polarization energy binned over a library of isomers. For the TB model, , whereas for the polarizable model, is defined in Eq. (40).

Image of FIG. 15.
FIG. 15.

Histogram of the components of the electron-water polarization energy for the polarizable model developed here, binned over a library of isomers. The quantities and are the total polarization energy and the polarization energy in the field of the neutral dipoles, respectively.

Tables

Generic image for table
Table I.

Parameters that determine the electron-water potential developed in this work.

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/content/aip/journal/jcp/130/12/10.1063/1.3089425
2009-03-25
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: The static-exchange electron-water pseudopotential, in conjunction with a polarizable water model: A new Hamiltonian for hydrated-electron simulations
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/12/10.1063/1.3089425
10.1063/1.3089425
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