Helium dimers in the d³Σ⁺_u excited electronic state with potential energy > 24 eV and radiative lifetime of 25 ns have been generated in a microcavity plasma jet and rotationally cooled by supersonic expansion in vacuum. The dynamic process of cooling is recorded by imaging the axis of expansion onto the slit of Czerny-Turner spectrometer, yielding spatial-temporal spectrograms of d³Σ⁺_u→b³Π_g (v′, v")=(0, 0) emission. Analysis of the data shows the spatial-temporal evolution of the rotational temperature to be a damped sinusoid that reaches a minimum value of 100K. This reproducible behavior is attributed to the reflection of electrons from a virtual cathode located downstream of the nozzle and indicates that the spatially-averaged electron density is 10⁸ cm⁻³. We present this observed rotational temperature oscillation during the supersonic cooling process as an example of the potential of our supersonic microplasma expansion as a tool to explore physical dynamics in diatomic molecules having high excitation energies and small lifetimes.

We investigate the dynamics of the photodissociation of ICN^–(Ar)_n and BrCN^–(Ar)_n following electronic excitation to states that dissociate into X^– + CN and X^* + CN^– (X = I or Br) using classical dynamics approaches. Observations made from previous experiments and calculations of these anions demonstrated that non-adiabatic effects are important in the photodissociation process and are reflected in the branching ratios of the photoproducts.S. Case, E. M. Miller, J. P. Martin, Y. J. Lu, L. Sheps, A. B. McCoy, and W. C. Lineberger, Angew. Chem., Int. Ed. 51, 2651 (2012).^,B. Opoku−Agyeman, A. S. Case, J. H. Lehman, W. Carl Lineberger and A. B. McCoy, J. Chem Phys. 141, 084305 (2014).he addition of an argon atom is expected to shift the relative energies of these excited states, thereby altering the product branching. Interestingly, experimental studies show that electronically exciting ICN^– solvated with even a single argon atom leads to a small fraction of the products recombine to form ICN^–.^aIn this study, the dynamics are carried out using classical mechanics, treating the non−adiabatic effect with a surface hopping algorithm.J. C. Tully, J. Chem Phys. 93, 1061 (1990).e assess the accuracy of this approach by first calculating the branching ratios for the bare anions and comparing the results to those from quantum dynamics calculations.^a,b B. Opoku-Agyeman, A. S. Case, J. H. Lehman, W. Carl Lineberger and A. B. McCoy, J. Chem Phys. 141, 084305 (2014).TJ. C. Tully, J. Chem Phys. 93, 1061 (1990).W

The Water-Argon cluster is an important system of fundamental and practical interest. It is for example known to be one of the simplest systems capable of manifesting “hydrophobic interactions” and as such is an ideal candidate for the study of those interactions. On the fundamental level, it is a model system for the description of the intermolecular potential, rovibrational states and inelastic scattering of an atom and an asymmetric top van der Waal complex and thus may serve as a test to perform similar work on other systems. Additionally, the description of the H₂O-Ar intermolecular interaction is an important initial step to a deeper understanding of the static and dynamical properties of condensed phases such H₂O doped in large (Ar)_N clusters. We investigate in this work the H₂O-Ar cluster on a global potential energy surface recently generated. We thus compute the rovibrational energy levels of the cluster in the rigid rotor approximation and in full dimensionality using the MCTDH improved relaxation method and compare our results with available experimental measurements and previous calculations. Then, we present inelastic scattering cross-sections of H₂O+Ar collisions obtained in the rigid rotor approximation using time-independent method and time-dependent method, and compare where available results with previous calculations. Finally, we will discuss the extension of the scattering calculations to the full dimensional case and the prospect of studying rovibrational relaxation within accurate time-dependent quantum calculations on similar systems or clusters.

Benzyl radical (C₆H₅CH₂) is a crucial intermediate in the combustion and pyrolysis of substituted aromatic species that are common both in modern gasoline and potential future biofuels. The decomposition of benzyl radical is complicated and has been shown by isotopic labeling to require interesting isomerizations pathways. To better understand these pathways, a set of C₇H₇ radicals has been studied in a heated micro-reactor. Through multiple experiments, it has be shown that benzyl radical and cycloheptatrienyl (tropyl) radical (c-C₇H₇) do not interconvert, even at temperatures where both have completely thermally decomposed. To confirm this, tropyl radical has been studied directly and its pyrolysis is quite simple, only cyclopentadienyl radical (c-C₅H₅) and acetylene (HCCH) are formed. Cyclopentadienyl radical then decomposes to acetylene and propargyl radical (HCCCH₂). These products have all been identified through use of tunable synchrotron radiation by confirming their respective photoionization spectra. Matrix isolation infrared (IR) spectroscopy has also been used to identity these products. A previously unanswered question in benzyl radical decomposition has been addressed by studying the pyrolysis of 2,5-norbornadiene, which indicates benzyl radical may decompose through a norbornadiene-like bicyclic radical intermediate. This pathways successfully predicts the correct isotopically labeled products observed previously during ¹³C labeled benzyl pyrolysis.

The Bellert group at Baylor University has developed a novel method for performing single photon initiated decomposition rearrangement reactions (SPIDRR) of organic molecules mediated by a transition metal cation. The advantage that SPIDRR affords is the direct measurement of first order microcanonical rate constants, k(E), determined at resolved internal energies. Furthermore, the SPIDRR technique measures kinetic details of exothermic reactions where product production is limited only by submerged activation barriers (kinetic barriers that are at energies below the separated reactant limit). Thus, such reactions approach unit efficiency, are thermodynamically driven, and are of greater relevance to catalytic research. Direct measurements of k(E) values extend to isotopically labelled species that provide direct measurement of the kinetic isotope effect (KIE), furnishing unique insight into the mechanistic details of a reaction. This talk presents results from the visible photon initiated, Ni⁺ induced decarbonylation reaction of propionaldehyde. Here a rather unique energy dependent behavior of the measured rate constants was observed and attributed to a dynamic competition between parallel reaction coordinates available to the photo-excited precursor. RRKM calculations in concert with high level DFT is used to support and further experimental results.

Alzheimer’s Disease (AD) is a neurodegenerative disorder that results from the formation of beta-amyloid plaques in the brain that trigger the known symptoms of memory loss in AD patients. The beta-amyloid plaques are formed by the proteolytic cleavage of the amyloid precursor protein (APP) by the proteases BACE1 and gamma-secretase. These enzyme-facilitated cleavages lead to the production of beta-amyloid fragments that aggregate to form plaques, which ultimately lead to neuronal cell death. Recent detergent protein extraction studies suggest that BACE1 protein forms a dimer that has significantly higher catalytic activity than its monomeric counterpart. In this contribution, we examine the dimerization hypothesis of BACE1 in cultured HEK293 cells using complementary fluorescence spectroscopy and microscopy methods. Cells were transfected with a BACE1-EGFP fusion protein construct and imaged using confocal, and differential interference contrast to monitor the localization and distribution of intracellular BACE1. Complementary fluorescence lifetime and anisotropy measurements enabled us to examine the conformational and environmental changes of BACE1 as a function of substrate binding. Using fluorescence correlation spectroscopy, we also quantified the diffusion coefficient of BACE1-EGFP on the plasma membrane as a means to test the dimerization hypothesis as a fucntion of substrate-analog inhibitition. Our results represent an important first towards examining the substrate-mediated dimerization hypothesis of BACE1 in live cells.

Novel donor-acceptor nanostructures were synthesized via covalent synthesis and/or UV cross-linking method. Their photoinduced dynamics were investigated with ultrafast transient absorption (TA) spectroscopy. These new nanostructures are made with the strategy in mind to reduce manufacturing steps in the process of fabricating an organic photovoltaic cell. By imitating the heterojunction interface within a fixed particle domain, several fabrication steps can be bypassed reducing cost and giving more applicability to other film deposition methods. Such applications include aerosol deposition and ink-jet printing. The systems that were studied by TA spectroscopy include PDIB core, PDIB-P3HT core-shell, and PDIB-PANT core-shell which range in size from 60 to 130 nm. Within the experimentally accessible spectra range there resides a region of ground state bleaching, stimulated emission, and excited-state absorption of both neutrals and anions. Control experiments have been carried out to assign these features. At high pump fluences the TA spectra of PDIB core alone also indicate an intramolecular charge separation. The TA spectroscopy results thus far suggest that the core-shells resemble the photoinduced dynamics of a standard film although the particles are dispersed in solution, which indicates the desired outcome of the work.

Methylammonium lead iodide (perovskite) is a leading candidate for use in next-generation solar cell devices. However, the photophysics responsible for its strong photovoltaic qualities are not fully understood. Ultrafast extreme ultraviolet (XUV) absorption was used to investigate electron and hole dynamics in perovskite by observing transitions from a common inner-shell level (I 4d) to the valence and conduction bands. Ultrashort (30 fs) pulses of XUV radiation with a broad spectrum (40-70 eV) were generated via high-harmonic generation using a tabletop instrument. Transient absorption measurements with visible pump and XUV probe directly observed the relaxation of charge carriers in perovskite after above-band excitation in the femtosecond and picosecond time ranges.