Picosecond photofragment spectroscopy. II. The overtone initiated unimolecular reaction H_2O_2(v_(OH)=5)→2OH

This paper, second in the series, reports on the picosecond time‐resolved photofragmentation of the overtone (v_(OH)=5) initiated reaction: HOOH+hν→2OH. The hydrogen peroxide is initially excited by way of a picosecond laser pulse to the fourth overtone level of the OH‐stretch local mode. The subsequent unimolecular reaction behavior is obtained by monitoring the laser‐induced fluorescence, caused by the picosecond probe–pulse electronic excitation of the OH radical photoproduct (in a given rotational state). The two pulses are scanned relative to one another in time thereby mapping out the product yield for the given delay‐time interval. The resultant product formation behavior is found to be nonexponential, and may be modeled as a biexponential rise. Furthermore, the quasibiexponential behavior is sensitive to the exact excitation wavelength—slight variations of which result in large changes in the two time constants and the relative amplitudes of the fast and slow components. These experiments give direct evidence for the inhomogeneous nature of the overtone transition on the picosecond time scale, and provide the dissociation rate contribution to the homogeneous width (0.05–0.15 cm^(−1)). The apparent width for the main band feature is about 200 cm^(−1). The rate of product formation (magnitude and form) is interpreted in terms of statistical and nonstatistical theories. The limitations of the applicability of each model is discussed. The fluctuations of the fitting parameters as a function of excitation wavelength may be simulated by a statistical model which considers all possible discrete optical transitions within the simulated laser bandwidth and the details of product formation from each state. For a nonstatistical interpretation, the biexponential form reflects a division of the vibrational phase space, and this is discussed in the spirit of a kinetic model. Finally, experimental results are reported for direct UV initiated photofragmentation. The observed dynamics indicate that a very different type of potential surface (repulsive) is involved, in contrast to the overtone initiated dissociation, which takes place on the ground state surface

Phase resetting reveals network dynamics underlying a bacterial cell cycle

Genomic and proteomic methods yield networks of biological regulatory interactions but do not provide direct insight into how those interactions are organized into functional modules, or how information flows from one module to another. In this work we introduce an approach that provides this complementary information and apply it to the bacterium Caulobacter crescentus, a paradigm for cell-cycle control. Operationally, we use an inducible promoter to express the essential transcriptional regulatory gene ctrA in a periodic, pulsed fashion. This chemical perturbation causes the population of cells to divide synchronously, and we use the resulting advance or delay of the division times of single cells to construct a phase resetting curve. We find that delay is strongly favored over advance. This finding is surprising since it does not follow from the temporal expression profile of CtrA and, in turn, simulations of existing network models. We propose a phenomenological model that suggests that the cell-cycle network comprises two distinct functional modules that oscillate autonomously and couple in a highly asymmetric fashion. These features collectively provide a new mechanism for tight temporal control of the cell cycle in C. crescentus. We discuss how the procedure can serve as the basis for a general approach for probing network dynamics, which we term chemical perturbation spectroscopy (CPS)

Ultrafast resonant optical scattering from single gold nanorods: Large nonlinearities and plasmon saturation

We measure nonlinear optical scattering from individual Au nanorods excited by ultrafast laser pulses on resonance with their longitudinal plasmon mode. Isolating single rods removes inhomogeneous broadening and allows the measurement of a large nonlinearity, much greater than that of nanorod ensembles. Surprisingly, the ultrafast nonlinearity can be attributed entirely to heating of conduction electrons and does not exhibit any response associated with coherent plasmon oscillation. This indicates a previously unobserved damping of strongly driven plasmons.Comment: Revised tex

Single-gene tuning of Caulobacter cell cycle period and noise, swarming motility, and surface adhesion

We established that the sensor histidine kinase DivJ has an important role in the regulation of C. crescentus cell cycle period and noise. This was accomplished by designing and conducting single-cell experiments to probe the dependence of cell cycle noise on divJ expression and constructing a simplified cell cycle model that captures the dependence of cell cycle noise on DivJ with molecular details.In addition to its role in regulating the cell cycle, DivJ also affects polar cell development in C. crescentus, regulating swarming motility and surface adhesion. We propose that pleiotropic control of polar cell development by the DivJ–DivK–PleC signaling pathway underlies divJ-dependent tuning of cell swarming and adhesion behaviors.We have integrated the study of single-cell fluorescence dynamics with a kinetic model simulation to provide direct quantitative evidence that the DivJ histidine kinase is localized to the cell pole through a dynamic diffusion-and-capture mechanism during the C. crescentus cell cycle

Generation of Robust Entanglement in Plasmonically Coupled Quantum Dots Driven by Quantum Squeezed Light

Our cavity quantum electrodynamics calculations demonstrate generation of steady-state entanglement between a plasmonically coupled pair of quantum dots by using single-mode squeezed light source. We show that strong coupling of plasmons to the incoming light source and the pairwise nature of squeezed photon generation enable the formation of entanglement between the initially unexcited quantum dots. The entanglement of quantum dots, measured as concurrence, can be improved replacing a pulsed source of light to continuous pumping of squeezed photons. Unlike previously introduced schemes the concurrence is robust against variations in the system parameters. Specifically, the generation of entanglement does not rely on fine tuning of plasmon quantum dot coupling. This work provides a new perspective for robust entangled state preparation in open quantum systems