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Ring polymer molecular dynamics beyond the linear response regime: Excess electron injection and trapping in liquids
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10.1063/1.3292576
/content/aip/journal/jcp/132/3/10.1063/1.3292576
http://aip.metastore.ingenta.com/content/aip/journal/jcp/132/3/10.1063/1.3292576
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

A typical RPMD trajectory for cold electron injection into supercritical helium. (a) The time series for the lowest excess electron eigenenergies (black) and the ring polymer radius of gyration (red). (b) Snapshots of the ring polymer (black) and solvent configurations from the RPMD trajectory. [(c) and (d)] The corresponding snapshots of the ground state (c) and first excited state (d) excess electron wavefunctions, visualized as 95% isosurfaces.

Image of FIG. 2.
FIG. 2.

Ring polymer radius of gyration following (a) cold injection and (b) hot injection of the excess electron into helium. The contour plot indicates the distribution of from the ensemble of RPMD trajectories, the heavy colored lines indicate the nonequilibrium average taken over trajectories , and the black dashed line indicates the average from an equilibrium simulation.

Image of FIG. 3.
FIG. 3.

A typical RPMD trajectory for hot electron injection into supercritical helium. (a) The time series for the lowest excess electron eigenenergies (black) and the ring polymer radius of gyration (red). (b) Snapshots of the ring polymer (black) and solvent configurations from the RPMD trajectory. [(c) and (d)] The corresponding snapshots of the ground state (c) and first excited state (d) excess electron wavefunctions.

Image of FIG. 4.
FIG. 4.

Time-resolved radial distribution function for the helium atoms with respect to the electron ring polymer centroid for (a) cold injection and (b) hot injection. In both parts, the contour line indicates 80% of the average solvent density. The dashed line in part (a) indicates the outward solvent compression wave following electron localization.

Image of FIG. 5.
FIG. 5.

The four lowest electron eigenenergies, obtained from the nonequilibrium average for RPMD trajectories following cold (blue) and hot (red) injection into the helium fluid. The black curve shows the corresponding ground-state result from the cold injection simulations with 4096 helium atoms. The black line exhibits a lower initial ground-state energy for the electron because the larger system size supports larger solvent density fluctuations in the neat fluid, even at the same average fluid density.

Image of FIG. 6.
FIG. 6.

Time-resolved radial distribution function following cold injection in the larger simulations with 4096 helium atoms, to be compared with Fig. 4(a).

Image of FIG. 7.
FIG. 7.

An illustrative cold injection trajectory in helium, showing the time series for (a) various energy components and (b) the ring polymer radius of gyration. In part (a), the blue curve presents , the sum of the solvent kinetic energy term and the solvent-solvent potential energy term, the red curve plots the electronc ground-state energy , the gray curve plots other low-lying electronic eigenenergies, and the heavy black curve plots the ground-state Born–Oppenheimer Hamiltonian, . Energy components are shifted by constant values for graphical clarity.

Image of FIG. 8.
FIG. 8.

An illustrative hot injection trajectory in helium, presented as in Fig. 7.

Image of FIG. 9.
FIG. 9.

The nonequilibrium average temperature for the helium solvent atoms (dashed) and for the ring polymer beads (solid) following cold electron injection. (a) Results obtained over 1 ps using 1024 ring polymer beads and (b) obtained for a shorter period using 512 (blue), 1024 (black), and 2048 (red) ring polymer beads. Error bars indicate the standard deviation of the mean.

Image of FIG. 10.
FIG. 10.

Ring polymer radius of gyration following excess electron injection in water. The contour plot indicates the distribution of from the ensemble RPMD trajectories for hot injection, the heavy lines indicate the nonequilibrium average taken over cold injection (blue) and hot injection (red) trajectories.

Image of FIG. 11.
FIG. 11.

Solvent dynamics following cold electron injection into water. (a) The time-resolved electron-hydrogen radial distribution function . (b) The time-resolved electron-oxygen radial distribution function .

Image of FIG. 12.
FIG. 12.

Solvent dynamics following hot electron injection into water. (a) The time-resolved electron-hydrogen radial distribution function . (b) The time-resolved electron-oxygen radial distribution function .

Image of FIG. 13.
FIG. 13.

The four lowest electron eigenenergies, obtained from the nonequilibrium average for RPMD trajectories following cold (blue) and hot (red) injection into the liquid water.

Image of FIG. 14.
FIG. 14.

Transient electron absorption spectra for cold (blue) and hot (red) excess electron injection into water, normalized by the maximum value. Spectra for each waiting time are vertically shifted for clarity.

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/content/aip/journal/jcp/132/3/10.1063/1.3292576
2010-01-20
2014-04-23
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Ring polymer molecular dynamics beyond the linear response regime: Excess electron injection and trapping in liquids
http://aip.metastore.ingenta.com/content/aip/journal/jcp/132/3/10.1063/1.3292576
10.1063/1.3292576
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