Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-pi(1)*; S-1 state) and the shorter (1 pi-pi(1)*; S-2 state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S-2 state relative to the ground state. Raman excitation profiles of PQ (400-1800 cm(-1)) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C-2 nu symmetry constraint on the S-2 state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling. (C) 2015 AIP Publishing LLC.

Direct Observation of Thermal Equilibrium of Excited Triplet States of 9,10-Phenanthrenequinone. A Time-Resolved Resonance Raman Study

The photochemistry of aromatic ketones plays a key role in various physicochemical and biological processes, and solvent polarity can be used to tune their triplet state properties. Therefore, a comprehensive analysis of the conformational structure and the solvent polarity induced energy level reordering of the two lowest triplet states of 9,10-phenanthrenequinone (PQ) was carried out using nanosecond-time-resolved absorption (ns-TRA), time-resolved resonance Raman (TR3) spectroscopy, and time dependent-density functional theory (TD-DFT) studies. The ns-TRA of PQ in acetonitrile displays two bands in the visible range, and these two bands decay with similar lifetime at least at longer time scales (mu s). Interestingly, TR3 spectra of these two bands indicate that the kinetics are different at shorter time scales (ns), while at longer time scales they followed the kinetics of ns-TRA spectra. Therefore, we report a real-time observation of the thermal equilibrium between the two lowest triplet excited states of PQ assigned to n pi* and pi pi* of which the pi pi* triplet state is formed first through intersystem crossing. Despite the fact that these two states are energetically close and have a similar conformational structure supported by TD-DFT studies, the slow internal conversion (similar to 2 ns) between the T-2(1(3)n pi*) and T-1(1(3)pi pi*) triplet states indicates a barrier. Insights from the singlet excited states of PQ in protic solvents J. Chem. Phys. 2015, 142, 24305] suggest that the lowest n pi* and pi pi* triplet states should undergo hydrogen bond weakening and strengthening, respectively, relative to the ground state, and these mechanisms are substantiated by TD-DFT calculations. We also hypothesize that the different hydrogen bonding mechanisms exhibited by the two lowest singlet and triplet excited states of PQ could influence its ISC mechanism.

Imaging properties of coherent anti-Stokes Raman scattering microscope

The coherent anti-Stokes Raman scattering (CARS) microscope with the combination of confocal and CARS techniques is a remarkable alternative for imaging chemical or biological specimens that neither fluoresce nor tolerate labelling. CARS is a nonlinear optical process, the imaging properties of CARS microscopy will be very different from the conventional confocal microscope. In this paper, the intensity distribution and the polarization property of the optical field near the focus was calculated. By using the Green function, the precise analytic solution to the wave equation of a Hertzian dipole source was obtained. We found that the intensity distributions vary considerably with the different experimental configurations and the different specimen shapes. So the conventional description of microscope (e.g. the point spread function) will fail to describe the imaging properties of the CARS microscope.

The intensity distributions of collected signals in coherent anti-Stokes Raman scattering microscopy

Coherent anti-Stokes Raman scattering (CARS) microscopy with the combining of confocal and CARS techniques is a remarkable alternative for imaging chemical or biological specimens that neither fluoresce nor tolerate labeling. The CARS is a nonlinear optical process, the imaging properties of CARS microscopy will be very different from the conventional confocal microscopy. In this paper, we calculated the propagation of CARS signals by using the wave equation in medium and the slowly varying envelope approximation (SVEA), and find that the intensity angular distributions vary considerably with the different experimental configurations and the different specimen shapes. So the conventional description of microscopy (e.g.. the point spread function) will fail to descript the imaging properties of CARS microscopy. (c) 2004 Elsevier B.V. All rights reserved.

Surface-enhanced Raman scattering substrate fabricated by femtosecond laser direct writing

We report the fabrication of a novel surface-enhanced Raman scattering (SERS) substrate with a controllable enhancement factor (EF) using femtosecond laser direct writing on Ag+-doped phosphate glass followed by chemical plating at similar to 40 degrees C. Silver seeds were first photoreduced using a femtosecond laser in a laser-irradiated area and then transformed into silver nanoparticles of suitable size for SERS application in the subsequent chemical plating. Rhodamine 6G was used as a probing molecule to investigate the enhancement effect of a Raman signal on the substrate. Nearly homogenous enhancement of the Raman signal over the Substrate was achieved, and the EF of the substrate was controlled to some extent by adjusting fabrication parameters. Moreover, the ability of forming a SERS platform in an embedded microfluidic chamber would be of great use for establishing a compact lab-on-a-chip device based on Raman analysis.

Fast growing mode of stimulated Raman scattering in a pure three-wave process

Stimulated Raman scattering (SRS) of a relativistic laser in plasmas is studied in the framework of the standard equation set of a three-wave process. As far as every wave involved in the process is concerned, its evolution has two aspects: time-dependent amplitude and time-dependent frequency. These two aspects affect each other. Strict analysis and numerical experiment on the full three-wave equation set reveal that a fast growing mode of the instability, which could reach a balance or saturation point during a period far shorter than an estimation based on conventional analysis, could take place in a standard three-wave process without coupling with a fourth wave. This fast growing mode is found to stem from the constraint set by the background density on the amplitude of the driven Langmuir wave. The effect of various parameters on the development of the SRS instability is studied by numerical calculation of the history of the instability in different cases. (c) 2007 American Institute of Physics.

Hierarchical electrohydrodynamic structures for surface-enhanced Raman scattering.

Surface enhanced Raman scattering (SERS) is a well-established spectroscopic technique that requires nanoscale metal structures to achieve high signal sensitivity. While most SERS substrates are manufactured by conventional lithographic methods, the development of a cost-effective approach to create nanostructured surfaces is a much sought-after goal in the SERS community. Here, a method is established to create controlled, self-organized, hierarchical nanostructures using electrohydrodynamic (HEHD) instabilities. The created structures are readily fine-tuned, which is an important requirement for optimizing SERS to obtain the highest enhancements. HEHD pattern formation enables the fabrication of multiscale 3D structured arrays as SERS-active platforms. Importantly, each of the HEHD-patterned individual structural units yield a considerable SERS enhancement. This enables each single unit to function as an isolated sensor. Each of the formed structures can be effectively tuned and tailored to provide high SERS enhancement, while arising from different HEHD morphologies. The HEHD fabrication of sub-micrometer architectures is straightforward and robust, providing an elegant route for high-throughput biological and chemical sensing.