Efficiency Limits of Energy Conversion by Light-Driven Redox Chains.

The conversion of absorbed sunlight to spatially separated electron-hole pairs is a crucial outcome of natural photosynthesis. Many organisms achieve near-unit quantum yields of charge separation (one electron-hole pair per incident photon) by dissipating as heat more than half of the light energy that is deposited in the primary donor. Might alternative choices have been made by Nature that would sacrifice quantum yield in favor of producing higher energy electron/hole pairs? Here, we use a multisite electron hopping model to address the kinetic and thermodynamic compromises that can be made in electron transfer chains, with the aim of understanding Nature's choices and opportunities in bioinspired energy-converting systems.

Fluence-Dependent Photoinduced Charge Transfer Dynamics in Polymer-Wrapped Semiconducting Single-Walled Carbon Nanotubes.

Because an individual single-walled carbon nanotube (SWNT) can absorb multiple photons, the exciton density within a single tube depends upon excitation conditions. In SWNT-based energy conversion systems, interactions between excitons and charges make it possible for multiple types of charge transfer reactions. We exploit a SWNT-molecular donor-acceptor hybrid system (-PBN(b)-Ph-PDI-[(6,5) SWNT]) that fixes spatial organization and stoichiometry of perylene diimide (PDI) electron acceptors on the nanotube surface, to elucidate how excitation fluence affects ultrafast charge separation (CS) and the nature of charge recombination (CR) dynamics triggered upon SWNT near-infrared excitation.

Band gap opening of metallic single-walled carbon nanotubes via noncovalent symmetry breaking.

Covalent bonding interactions determine the energy-momentum (-) dispersion (band structure) of solid-state materials. Here, we show that noncovalent interactions can modulate the - dispersion near the Fermi level of a low-dimensional nanoscale conductor. We demonstrate that low energy band gaps may be opened in metallic carbon nanotubes through polymer wrapping of the nanotube surface at fixed helical periodicity.

Electron Spin Polarization and Rectification Driven by Chiral Perylene Diimide-Based Nanodonuts.

The chirality-induced spin selectivity (CISS) effect allows thin-film layers of chiral conjugated molecules to function as spin filters at ambient temperature. Through solvent-modulated dropcasting of chiral l- and d-perylene diimide (PDI) monomeric building blocks, two types of aggregate morphologies, nanofibers and nanodonuts, may be realized. Spin-diode behavior is evidenced in the nanodonut structures.