Femtosecond real-time probing of reactions. XI. The elementary OClO fragmentation

Femtosecond reaction dynamics of OClO in a supersonic molecular beam are reported. The system is excited to the A 2A2 state with a femtosecond pulse, covering a range of excitation in the symmetric stretch between v1=17 to v1=11 (308–352 nm). A time-delayed femtosecond probe pulse ionizes the OClO, and OClO + is detected. This ion has not been observed in previous experiments because of its ultrafast fragmentation. Transients are reported for the mass of the parent OClO as well as the mass of the ClO. Apparent biexponential decays are observed and related to the fragmentation dynamics: OClO+hnu-->(OClO)[double-dagger]*-->ClO+O -->Cl+O2 . Clusters of OClO with water (OClO)n (H2O)m with n from 1 to 3 and m from 0 to 3 are also observed. The dynamics of the fragmentation reveal the nuclear motions and the electronic coupling between surfaces. The time scale for bond breakage is in the range of 300–500 fs, depending on v1; surface crossing to form new intermediates is a pathway for the two channels of fragmentation: ClO+O (primary) and Cl+O2 (minor). Comparisons with results of ab initio calculations are made

Femtosecond real-time probing of reactions. IX. Hydrogen-atom transfer

The real-time dynamics of hydrogen-atom-transfer processes under collisionless conditions are studied using femtosecond depletion techniques. The experiments focus on the methyl salicylate system, which exhibits ultrafast hydrogen motion between two oxygen atoms due to molecular tautomerization, loosely referred to as intramolecular ''proton'' transfer. To test for tunneling and mass effects on the excited potential surface, we also studied deuterium and methyl-group substitutions. We observe that the motion of the hydrogen, under collisionless conditions, takes place within 60 fs. At longer times, on the picosecond time scale, the hydrogen-transferred form decays with a threshold of 15.5 kJ/mol; this decay behavior was observed up to a total vibrational energy of approximately 7200 cm-1. The observed dynamics provide the global nature of the motion, which takes into account bonding before and after the motion, and the evolution of the wave packet from the initial nonequilibrium state to the transferred form along the O-H-O reaction coordinate. The vibrational periods (2pi/omega) of the relevant modes range from 13 fs (the OH stretch) to 190 fs (the low-frequency distortion) and the motion involves (in part) these coordinates. The intramolecular vibrational-energy redistribution dynamics at longer times are important to the hydrogen-bond dissociation and to the nonradiative decay of the hydrogen-transferred form

Exploring, tailoring, and traversing the solution landscape of a phase-shaped CARS process

Pulse shaping techniques are used to improve the selectivity of broadband CARS experiments, and to reject the overwhelming background. Knowledge about the fitness landscape and the capability of tailoring it is crucial for both fundamental insight and performing an efficient optimization of phase shapes. We use an evolutionary algorithm to find the optimal spectral phase of the broadband pump and probe beams in a background-suppressed shaped CARS process. We then investigate the shapes, symmetries, and topologies of the landscape contour lines around the optimal solution and also around the point corresponding to zero phase. We demonstrate the significance of the employed phase bases in achieving convex contour lines, suppressed local optima, and high optimization fitness with a few (and even a single) optimization parameter

Implementation of vibrational phase contrast coherent anti-Stokes Raman scattering microscopy

Detection of molecules using vibrational resonances in the fingerprint region for narrowband coherent anti-Stokes Raman scattering (CARS) is challenging. The spectrum is highly congested resulting in a large background and a reduced specificity. Recently we introduced vibrational phase contrast CARS (VPC-CARS) microscopy as a technique capable of detecting both the amplitude and phase of the CARS signal, providing background-free images and high specificity. In this paper we present a new implementation of VPC-CARS based on a third-order cascaded phase-preserving chain, where the CARS signal is generated at a single (constant) wavelength independent of the vibrational frequency that is addressed. This implementation will simplify the detection side considerably

A route to sub-diffraction-limited CARS Microscopy

We theoretically investigate a scheme to obtain sub-diffraction-limited resolution in coherent anti-Stokes Raman scattering (CARS) microscopy. We find using density matrix calculations that the rise of vibrational (Raman) coherence can be strongly suppressed, and thereby the emission of CARS signals can be significantly reduced, when pre-populating the corresponding vibrational state through an incoherent process. The effectiveness of pre-populating the vibrational state of interest is investigated by considering the excitation of a neighbouring vibrational (control) state through an intense, mid-infrared control laser. We observe that, similar to the processes employed in stimulated emission depletion microscopy, the CARS signal exhibits saturation behaviour if the transition rate between the vibrational and the control state is large. Our approach opens up the possibility of achieving chemically selectivity sub-diffraction-limited spatially resolved imaging

Observation of nonlinear bands in near-field scanning optical microscopy of a photonic-crystal waveguide

We have measured the photonic bandstructure of GaAs photonic-crystal waveguides with high energy and momentum resolution using near-field scanning optical microscopy. Intriguingly, we observe additional bands that are not predicted by eigenmode solvers, as was recently demonstrated by Huisman et al. [Phys. Rev. B 86, 155154 (2012)]. We study the presence of these additional bands by performing measurements of these bands while varying the incident light power, revealing a non-linear power dependence. Here, we demonstrate experimentally and theoretically that the observed additional bands are caused by a waveguide-specific near- field tip effect not previously reported, which can significantly phase-modulate the detected field.Comment: 6 pages, 5 figure

Coherent Control of the Exciton Dynamics in the FMO Protein

We have achieved first steps toward coherent control of excitonic energy migration in the FMO pigment-protein complex, by combining femtosecond pulse shaping with a feedback loop using an evolutionary algorithm. The experimental conditions achieved, with a rotating sample, a cryostat, and a pulse shaper, are sufficient for closed loop optimizations.</p

Blame, Symbolic Stigma and HIV Misconceptions are Associated with Support for Coercive Measures in Urban India

This study was designed to examine the prevalence of stigma and its underlying factors in two large Indian cities. Cross-sectional interview data were collected from 1,076 non-HIV patients in multiple healthcare settings in Mumbai and Bengaluru, India. The vast majority of participants supported mandatory testing for marginalized groups and coercive family policies for PLHA, stating that they “deserved” their infections and “didn’t care” about infecting others. Most participants did not want to be treated at the same clinic or use the same utensils as PLHA and transmission misconceptions were common. Multiple linear regression showed that blame, transmission misconceptions, symbolic stigma and negative feelings toward PLHA were significantly associated with both stigma and discrimination. The results indicate an urgent need for continued stigma reduction efforts to reduce the suffering of PLHA and barriers to prevention and treatment. Given the high levels of blame and endorsement of coercive policies, it is crucial that such programs are shaped within a human rights framework

Spatially dependent Rabi oscillations: an approach to sub-diffraction-limited CARS microscopy

We present a theoretical investigation of coherent anti-Stokes Raman scattering (CARS) that is modulated by periodically depleting the ground state population through Rabi oscillations driven by an additional control laser. We find that such a process generates optical sidebands in the CARS spectrum and that the frequency of the sidebands depends on the intensity of the control laser light field. We show that analyzing the sideband frequency upon scanning the beams across the sample allows one to spatially resolve emitter positions where a spatial resolution of 65 nm, which is well below the diffraction-limit, can be obtained

Active and passive control of zinc phthalocyanine photodynamics

In this work we report on the ultrafast photodynamics of the photosensitizer zinc phthalocyanine (ZnPc) and manipulation thereof. Two approaches are followed: active control via pulse shaping and passive control via strategic manipulation in the periphery of the molecular structure. The objective of both of these control experiments is the same: to enhance the yield of the functional pathway and to minimize loss channels. The aim of the active control experiments is to increase the intersystem crossing yield in ZnPc, which is important for application in photodynamic therapy (PDT). Pulse shaping allowed an improvement in triplet to singlet ratio of 15% as compared to a transform-limited pulse. This effect is ascribed to a control mechanism that utilizes multiphoton pathways to higher-lying states from where intersystem crossing is more likely to occur. The passive control experiments are performed on ZnPc derivatives deposited onto TiO2, serving as a model system of a dye-sensitized solar cell (DSSC). Modification of the anchoring ligand of the molecular structure resulted in an increased rate for electron injection into TiO2 and slower back electron transfer, improving the DSSC efficiency