Ultrafast Time-Resolved X-ray Absorption Spectroscopy of Ferrioxalate Photolysis with a Laser Plasma X-ray Source and Microcalorimeter Array.

The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. These results are compared to previously published transient X-ray absorption measurements on the same reaction and found to be consistent with the results from Ogi et al. and inconsistent with the results of Chen et al. ( Ogi , Y. ; et al. Struct. Dyn. 2015 , 2 , 034901 ; Chen , J. ; Zhang , H. ; Tomov , I. V. ; Ding , X. ; Rentzepis , P. M. Chem. Phys. Lett. 2007 , 437 , 50 - 55 ). We provide quantitative limits on the Fe-O bond length change. Finally, we review potential improvements to our measurement technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.

Femtosecond Measurements Of Size-Dependent Spin Crossover In Fe(II)(pyz)Pt(CN)4 Nanocrystals.

We report a femtosecond time-resolved spectroscopic study of size-dependent dynamics in nanocrystals (NCs) of Fe(pyz)Pt(CN)4. We observe that smaller NCs (123 or 78 nm cross section and <25 nm thickness) exhibit signatures of spin crossover (SCO) with time constants of ∼5-10 ps whereas larger NCs with 375 nm cross section and 43 nm thickness exhibit a weaker SCO signature accompanied by strong spectral shifting on a ∼20 ps time scale. For the small NCs, the fast dynamics appear to result from thermal promotion of residual low-spin states to high-spin states following nonradiative decay, and the size dependence is postulated to arise from differing high-spin vs low-spin fractions in domains residing in strained surface regions. The SCO is less efficient in larger NCs owing to their larger size and hence lower residual LS/HS fractions. Our results suggest that size-dependent dynamics can be controlled by tuning surface energy in NCs with dimensions below ∼25 nm for use in energy harvesting, spin switching, and other applications.

Quantum confined electron-phonon interaction in silicon nanocrystals.

We study the micro-Raman spectra of colloidal silicon nanocrystals as a function of size, excitation wavelength, and excitation intensity. We find that the longitudinal optical (LO) phonon spectrum is asymmetrically broadened toward the low energy side and exhibits a dip or antiresonance on the high-energy side, both characteristics of a Fano line shape. The broadening depends on both nanocrystal size and Raman excitation wavelength. We propose that the Fano line shape results from interference of the optical phonon response with a continuum of electronic states that become populated by intraband photoexcitation of carriers. The asymmetry exhibits progressive enhancement with decreasing particle size and with increasing excitation energy for a given particle size. We compare our observations with those reported for p- and n-doped bulk Si, where Fano interference has also been observed, but we find opposite wavelength dependence of the asymmetry for the bulk and nanocrystalline Si. Our results have important implications for potentially controlling carrier energy relaxation channels in strongly confined Si nanocrystals.

Optically induced thermal gradients for protein characterization in nanolitre-scale samples in microfluidic devices.

Proteins are the most vital biological functional units in every living cell. Measurement of protein stability is central to understanding their structure, function and role in diseases. While proteins are also sought as therapeutic agents, they can cause diseases by misfolding and aggregation in vivo. Here we demonstrate a novel method to measure protein stability and denaturation kinetics, on unprecedented timescales, through optically-induced heating of nanolitre samples in microfluidic capillaries. We obtain protein denaturation kinetics as a function of temperature, and accurate thermodynamic stability data, from a snapshot experiment on a single sample. We also report the first experimental characterization of optical heating in controlled microcapillary flow, verified by computational fluid dynamics modelling. Our results demonstrate that we now have the engineering science in hand to design integrated all-optical microfluidic chips for a diverse range of applications including in-vitro DNA amplification, healthcare diagnostics, and flow chemistry.

Controlling piezoelectric response in semiconductor quantum dots via impulsive charge localization.

By direct observation of coherent acoustic phonons, we demonstrate a novel extrinsic piezoelectric response in colloidal CdSe semiconductor quantum dots. This response is driven by the migration of charges to the surface of the quantum dot on a vibrationally impulsive time scale. Surface- and fluence-dependent studies reveal that the observed carrier capture based piezo response is controllable and is at least an order of magnitude larger than the intrinsic piezo response of wurtzite CdSe.

Hydrated electrons at the water/air interface.

The dynamics of hydrated electrons at the water/air interface are investigated using time-resolved second-harmonic generation spectroscopy. Initial solvation occurs in approximately 1 ps, and the electron remains at the interface for >750 ps. The location of the electron relative to the dividing surface is investigated using surfactants, which show that the electron is hydrated in the interfacial region, below the dividing surface.

State-resolved manipulations of optical gain in semiconductor quantum dots: Size universality, gain tailoring, and surface effects.

Optical gain in strongly confined colloidal semiconductor quantum dots is measured using state resolved pump/probe spectroscopy. Though size tunable optical amplification has been previously reported for these materials, the influence of confinement enhanced multiexcitonic interactions has limited prior demonstrations to specific particle sizes or host media. Here we show that the influence of the interfering multiexcitonic interactions, and hence the development of optical gain, is dependent on the identity of the initially prescribed excitonic state. By maintaining a constant excitonic state in the size tunable electronic structure of these materials, we recover the predicted universal development of optical gain, reflected by size-independent occupation thresholds, and differential gains. In addition, we explicitly compare the influence of surface passivation on the development and lifetime of the optical gain. Furthermore, we introduce a general, state-resolved pumping scheme which enables control over the optical gain spectrum. The capacity to manipulate the optical gain spectra of these spherically confined systems is evident in both the measured stimulated emission and amplified spontaneous emission. We anticipate that state-resolved optical excitation will be a useful method of enabling the development and manipulation of optical gain in any quantized nanostructure.

Gain control in semiconductor quantum dots via state-resolved optical pumping.

Excitonic state-resolved optical pumping experiments were performed on strongly confined semiconductor quantum dots. We demonstrate for the first time that optical gain is dependent upon the initial excitonic state. By prescribing the specific multiexcitonic states which can create, block, and ultimately control optical gain spectra, we recover the theoretically predicted size independence, even in systems which previously showed zero gain. In addition, we show for the first time that stimulated emission in quantum dots can be controlled via specific multiexcitonic interactions.

State-resolved studies of biexcitons and surface trapping dynamics in semiconductor quantum dots.

Biexcitons in strongly confined, colloidal CdSe quantum dots were investigated with excitonic state selectivity combined with 10 fs temporal precision. Within the first 50 fs, the first excited state of the biexciton was observed. By 100 ps, mixed character biexcitons were observed, comprised of a core exciton and a surface trapped exciton. The size dependence of the biexciton binding energies is reported for these specific biexcitons. Analysis of the spectral signatures of each biexcitonic state yields a quantitative measure of enhanced excited state trapping rates at the surface of the quantum dots. By comparing the biexcitonic signals to the state-filling signals, we show that it is primarily the holes which are trapped at the interface on the 100 ps time scale.