Phonon-mediated and weakly size-dependent electron and hole cooling in CsPbBr3 nanocrystals revealed by atomistic simulations and ultrafast spectroscopy

We combine state-of-the-art ultrafast photoluminescence and absorption spectroscopy and nonadiabatic molecular dynamics simulations to investigate charge-carrier cooling in CsPbBr3 nanocrystals over a very broad size regime, from 0.8 to 12 nm. Contrary to the prevailing notion that polaron formation slows down charge-carrier cooling in lead-halide perovskites, no suppression of carrier cooling is observed in CsPbBr3 nanocrystals except for a slow cooling (over similar to 10 ps) of "warm" electrons in the vicinity (within similar to 0.1 eV) of the conduction band edge. At higher excess energies, electrons and holes cool with similar rates, on the order of 1 eV ps(-1) carrier(-1), increasing weakly with size. Our ab initio simulations suggest that cooling proceeds via fast phonon-mediated intraband transitions driven by strong and size-dependent electron-phonon coupling. The presented experimental and computational methods yield the spectrum of involved phonons and may guide the development of devices utilizing hot charge carriers

Comparative PCET Study of a Donor-Acceptor Pair Linked by Ionized and Nonionized Asymmetric Hydrogen-Bonded Interfaces

A Zn(II) porphyrin-amidinium is the excited state electron donor (D) to a naphthalene diimide acceptor (A) appended with either a carboxylate or sulfonate functionality. The two-point hydrogen bond (---[H+]---) formed between the amidinium and carboxylate or sulfonate establishes a proton-coupled electron transfer (PCET) pathway for charge transfer. The two D---[H+]---A assemblies differ only by the proton configuration within the hydrogen bonding interface. Specifically, the amidinium transfers a proton to the carboxylate to form a non-ionized amidine-carboxylic acid two-point hydrogen network whereas the amidinium maintains both protons when bound to the sulfonate functionality forming an ionized amidinium-sulfonate two-point hydrogen network. These two interface configurations within the dyads thus allow for a direct comparison of PCET kinetics for the same donor and acceptor juxtaposed by an ionized and non-ionized hydrogen-bonded interface. Analysis of PCET kinetics ascertained from transient absorption and transient emission spectroscopy reveal that the ionized interface is more strongly impacted by the local solvent environment, thus establishing that the initial static configuration of the proton interface is a critical determinant to the kinetics of PCET.Chemistry and Chemical Biolog

Ultrafast phase modulation in CdSe colloidal quantum wells

C

Energy Harvesting for Structural Health Monitoring Sensor Networks

This report has been developed based on information exchanges at a 2.5-day workshop on energy harvesting for embedded structural health monitoring (SHM) sensing systems that was held June 28-30, 2005, at Los Alamos National Laboratory. The workshop was hosted by the LANL/UCSD Engineering Institute (EI). This Institute is an education- and research-focused collaboration between Los Alamos National Laboratory (LANL) and the University of California, San Diego (UCSD), Jacobs School of Engineering. A Statistical Pattern Recognition paradigm for SHM is first presented and the concept of energy harvesting for embedded sensing systems is addressed with respect to the data acquisition portion of this paradigm. Next, various existing and emerging sensing modalities used for SHM and their respective power requirements are summarized, followed by a discussion of SHM sensor network paradigms, power requirements for these networks and power optimization strategies. Various approaches to energy harvesting and energy storage are discussed and limitations associated with the current technology are addressed. This discussion also addresses current energy harvesting applications and system integration issues. The report concludes by defining some future research directions and possible technology demonstrations that are aimed at transitioning the concept of energy harvesting for embedded SHM sensing systems from laboratory research to field-deployed engineering prototypes