1. Volume 4, Issue 5, Pages 1112-1127 (May 2018)
Plasmon-Mediated Electron Injection from Au Nanorods into MoS2: Traditional versus Photoexcitation Mechanism 
Zhaosheng Zhang, Lihong Liu, Wei-Hai Fang, Run Long, Marina V. Tokina, Oleg V. Prezhdo 
Chem 
Volume 4, Issue 5, Pages (May 2018)
DOI: /j.chempr
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2. Chem 2018 4, DOI: ( /j.chempr )
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3. Figure 1
The Simulation Cell Showing the Geometry of the Au100-(MoS2)12 System
(Top) Optimized at 0 K.
(Bottom) A representative geometry during the molecular dynamics run at 300 K. The gold nanorod used in current work mimics morphology of the experimental sample.21 Thermal fluctuations are much more pronounced in the gold nanorod than the MoS2 layer. The donor-acceptor separation increases and the Au100-MoS2 coupling decreases at the higher temperature.
Chem 2018 4, DOI: ( /j.chempr )
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4. Figure 2
Projected Density of States (PDOS) of the Au100-(MoS2)12 Hybrid Is Split Into Contributions from the Gold Antenna and the MoS2 Layer
The peaks marked by A and B correspond to the plasmon states whose charge densities are shown in Figures 3A and 3B, respectively.
Chem 2018 4, DOI: ( /j.chempr )
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5. Figure 3 Charge Densities for a Narrow Au Rod
(A–D) Plasmon-like states in the gold nanorod corresponding to peaks A and B in Figure 2 (A and B, respectively), the nanorod bulk-type state (C), and the electron acceptor state (D). The charge densities were obtained with the isosurface value of e/Bohr3. Photoexcited charge separation involves the excitation of surface plasmon-like states (A and B) that decay rapidly into bulk states (C). Subsequently, an electron is transferred into an MoS2 state (D). Note that both plasmon and bulk states are slightly delocalized onto MoS2, facilitating plasmon dephasing and charge transfer. The acceptor state is distributed on Mo atoms of the MoS2 monolayer.
(E and F) Charge-density projections on the z (E) and y (F) axes demonstrate that plasmon-like states extend much more outside the Au rod and are much smoother than the bulk state.
Chem 2018 4, DOI: ( /j.chempr )
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6. Figure 4 Spectral Density
Spectral density obtained by Fourier transform of the energies of the initial plasmon-like states (A) peak A and (B) peak B in Figure 2 and (C) the bulk state. The state densities are shown in Figures 3A–3C. Surface plasmons couple only to low-frequency phonons of gold, and gold bulk states also interact with higher frequency phonons.
Chem 2018 4, DOI: ( /j.chempr )
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7. Figure 5 Population Dynamics
Electron dynamics following excitation of the plasmon-like states marked by (A) peak A and (B) peak B in Figure 2 (densities are shown in Figures 3A and 3B). The surface plasmons decay rapidly into many bulk states of gold, which are exemplified in Figure 3C.
Chem 2018 4, DOI: ( /j.chempr )
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8. Figure 6 Line Broadening
(A) Density of states (DOS) of isolated Au100 and Au100 interacting with MoS2 in which A and B represent plasmon states and C represents bulk states.
(B–D) The fragment analysis of DOS (left) near the three peaks that provide fractions of KS orbital localized on Au100 in either isolated Au100 (vertical black sticks) or Au100 interacting with MoS2 (vertical red sticks). Peaks C, A, and B in (A) correspond to (B), (C), and (D), respectively, and represent one bulk and two plasmon states. The orbital charge densities, as denoted by the arrows, are shown on the right. Interaction with MoS2 splits the Au100 peak into two smaller peaks. The energy splitting between the two peaks characterizes the strength of the Au100-MoS2 interaction and is inversely proportional to the electron injection time (Table 1).
Chem 2018 4, DOI: ( /j.chempr )
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9. Figure 7 Electron-Vibrational Energy Relaxation
Semi-logarithmic plot of energy relaxation following excitation of the two plasmon-like states, marked as (A) peak A and (B) peak B in Figures 2 and 6. In both cases, the energy relaxation is slower than the plasmon decay into bulk states (Figure 5) and the ET (Table 1), indicating that excitation at surface plasmon energies can lead to efficient charge separation in Au-MoS2 hybrids.
Chem 2018 4, DOI: ( /j.chempr )
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10. Figure 8 Charge Densities for a Au Pyramid and Wide Rod
Charge density of plasmon-like states in the (A) Au20 pyramid and (B) Au27 nanorod in contact with MoS2. In contrast to the Au20-TiO2 system,25 in which the plasmon state density delocalizes over a large area of TiO2, here the plasmon tails are small and extend only onto the area of MoS2 immediately below Au because of weak interaction with the chemically saturated MoS2. The pyramid configuration has a larger contact area and a bigger tail.
Chem 2018 4, DOI: ( /j.chempr )
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