Time-Domain Ab Initio Modeling of Photoinduced Dynamics at Nanoscale Interfaces

Supplementary Data

• Download Supplemental Figures 1-7 as a single PDF, or see below.

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  Supplemental Figure 1. Photoinduced electron transfer (ET) dynamics from a PbSe quantum dot (QD) into a TiO₂ slab. The solid black, dashed blue, and dotted red lines represent the total, adiabatic, and nonadiabatic ET, respectively. The open circles are exponential fits with the time scales shown in the figure. Adapted with permission from J. Am. Chem. Soc. 133, 19240 (2011). Copyright 2011 American Chemical Society.

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  Supplemental Figure 2. Electron-hole recombination rate (k_ET) as a function of TiO₂-QD bridge length x and PbSe QD radius r. The dependence on the QD radius is partitioned into changes due to energy gap and donor-acceptor coupling. Adapted with permission from J. Phys. Chem. Lett. 5, 2941 (2014). Copyright 2014 American Chemical Society.

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  Supplemental Figure 3. Photoinduced ET dynamics from a CdSe QD into either a TiO₂ QD (left panel) or a TiO₂ nanobelt (right panel). The solid black, dashed red, and dash-dotted blue lines represent the total, adiabatic, and nonadiabatic ET, respectively. The brown lines show the exponential fits of the total ET data. Adapted with permission from Nano Lett. 14, 1790 (2014). Copyright 2014 American Chemical Society.

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  Supplemental Figure 4. (a) Charge densities of different photoexcited donor states and an acceptor state. The photoexcited states exhibit different degrees of delocalization onto TiO₂, ranging from 20% for E2 to 60% for E3, while the acceptor state is localized entirely within TiO₂. The delocalization of the donor states into TiO₂ reflects direct ET due to strong coupling between the two species. (b) Semilogarithmic plot of energy relaxation from the E1, E2, and E3 photoexcited states. The inverse of the slopes, shown as dashed lines, gives the relaxation time. (c) Average ET dynamics for the three photoexcited states. The solid black, dashed blue, and dotted red lines represent the total, adiabatic, and nonadiabatic ET, respectively. The empty circles show exponential fits of the total ET data. Adapted with permission from J. Am. Chem. Soc. 134, 14238 (2012). Copyright 2012 American Chemical Society.

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  Supplemental Figure 5. Dynamics of ET from a CdSe QD to C₆₀ with van der Waals contact, van der Waals contact with Li inside C₆₀, or covalent bonding between the CdSe QD and C₆₀. Adapted with permission from J. Phys. Chem. Lett. 4, 1 (2013). Copyright 2013 American Chemical Society.

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  Supplemental Figure 6. (Left and middle panels) Measured rates of ET from CdS, CdSe, and CdTe QDs to MB⁺ (red circles), MV²⁺ (blue triangles), and AQ (green diamonds) as functions of driving force, and predicted ET rates (lines) assuming different reorganization energy (λ) according to the conventional and Auger-assisted ET models. (Right panel) Evolution of electron, hole, and phonon energies, and the donor-acceptor energy gap (ΔG). Adapted with permission from Nano Lett. 14, 1263 (2014). Copyright 2014 American Chemical Society.

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  Supplemental Figure 7. (Upper panel) Time-dependent population of the electron and hole donor states in the P3HT-CNT system. The corresponding charge densities of the donor and acceptor orbitals for the hole and electron transfer are shown in the inset. (Lower panel) Projected density of states for P3HT and CNT. The inset shows the energy offsets between the donor and acceptor orbitals for the electron and hole transfer. Adapted with permission from Nano Lett. 14, 3335 (2014). Copyright 2014 American Chemical Society.