Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Capillary Effect on Vertically Excited Surface Wave in Circular Cylindrical Vessel

In a vertically oscillating circular cylindrical container, singular perturbation theory of two-time scale expansions was developed in inviscid fluids to investigate the motion of single free surface standing wave including the effect of surface tension.

Damping of Vertically Excited Surface Wave in Weakly Viscous Fluid

In a vertically oscillating circular cylindrical container, singular perturbation theory of two-time scale expansions is developed in weakly viscous fluids to investigate the motion of single free surface standing wave by linearizing the Navier-Stokes equation. The fluid field is divided into an outer potential flow region and an inner boundary layer region. The solutions of both two regions are obtained and a linear amplitude equation incorporating damping term and external excitation is derived. The condition to appear stable surface wave is obtained and the critical curve is determined. In addition, an analytical expression of damping coefficient is determined. Finally, the dispersion relation, which has been derived from the inviscid fluid approximation, is modified by adding linear damping. It is found that the modified results are reasonably closer to experimental results than former theory. Result shows that when forcing frequency is low, the viscosity of the fluid is prominent for the mode selection. However, when forcing frequency is high, the surface tension of the fluid is prominent.

Forcing of self-excited round jet diffusion flames

In this experimental and numerical study, two types of round jet are examined under acoustic forcing. The first is a non-reacting low density jet (density ratio 0.14). The second is a buoyant jet diffusion flame at a Reynolds number of 1100 (density ratio of unburnt fluids 0.5). Both jets have regions of strong absolute instability at their base and this causes them to exhibit strong self-excited bulging oscillations at welldefined natural frequencies. This study particularly focuses on the heat release of the jet diffusion flame, which oscillates at the same natural frequency as the bulging mode, due to the absolutely unstable shear layer just outside the flame. The jets are forced at several amplitudes around their natural frequencies. In the non-reacting jet, the frequency of the bulging oscillation locks into the forcing frequency relatively easily. In the jet diffusion flame, however, very large forcing amplitudes are required to make the heat release lock into the forcing frequency. Even at these high forcing amplitudes, the natural mode takes over again from the forced mode in the downstream region of the flow, where the perturbation is beginning to saturate non-linearly and where the heat release is high. This raises the possibility that, in a flame with large regions of absolute instability, the strong natural mode could saturate before the forced mode, weakening the coupling between heat release and incident pressure perturbations, hence weakening the feedback loop that causes combustion instability. © 2009 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Nonlinear Faraday Waves in a Parametrically Excited Circular Cylindrical Container

In the cylindrical coordinate system, a singular perturbation theory of multiple-scale asymptotic expansions was developed to study single standing water wave mode by solving potential equations of water waves in a rigid circular cylinder, which is subjec

Effect of surface tension on the mode selection of vertically excited surface waves in a circular cylindrical vessel

Singular perturbation theory of two-time-scale expansions was developed in inviscid fluids to investigate patternforming, structure of the single surface standing wave, and its evolution with time in a circular cylindrical vessel subject to a vertical oscillation. A nonlinear slowly varying complex amplitude equation, which involves a cubic nonlinear term, an external excitation and the influence of surface tension, was derived from the potential flow equation. Surface tension was introduced by the boundary condition of the free surface in an ideal and incompressible fluid. The results show that when forced frequency is low, the effect of surface tension on the mode selection of surface waves is not important. However, when the forced frequency is high, the surface tension cannot be neglected. This manifests that the function of surface tension is to cause the free surface to return to its equilibrium configuration. In addition, the effect of surface tension seems to make the theoretical results much closer to experimental results.

Surface waves in a vertically excited circular cylindrical container

The nonlinear free surface amplitude equation, which has been derived from the inviscid fluid by solving the potential equation of water waves with a singular perturbation theory in a vertically oscillating rigid circular cylinder, is investigated successively in the fourth-order Runge-Kutta approach with an equivalent time-step. Computational results include the evolution of the amplitude with time, the characteristics of phase plane determined by the real and imaginary parts of the amplitude, the single-mode selection rules of the surface waves in different forced frequencies, contours of free surface displacement and corresponding three-dimensional evolution of surface waves, etc. In addition, the comparison of the surface wave modes is made between theoretical calculations and experimental measurements, and the results are reasonable although there are some differences in the forced frequency.

Three-photon-excited upconversion luminescence of YVO4 single crystal by infrared femtosecond laser irradiation

We report on the upconversion luminescence of a pure YVO4 single crystal excited by an infrared femtosecond laser. The luminescent spectra show that the upconversion luminescence comes from the transitions from the lowest excited states T-3(1), T-3(2) to the ground state (1)A(1) of the VO43-. The dependence of the fluorescence intensity on the pump power density of laser indicates that the conversion of infrared irradiation to visible emission is dominated by three-photon excitation process. We suggest that the simultaneous absorption of three infrared photons promotes the VO43- to excited states, which quickly cascade down to lowest excited states, and radiatively relax to ground states, resulting in the broad characteristic fluorescence of VO43-. (c) 2005 Optical Society of America.

Few-cycle spatiotemporal soliton wave excited by filamentation of a femtosecond laser pulse in materials with anomalous dispersion

The nonlinear dynamics of 1.6-mu m fs laser pulses propagating in fused silica is investigated by employing a full-order dispersion model. Different from the x-wave generation in normally dispersive media, a few-cycle spatiotemporally compressed soliton wave is generated with the contrary contributions of anomalous group velocity dispersion (GVD) and self-phase-modulation. However, at the tailing edge of the pulse forms a shock wave which generates separate and strong supercontinuum peaked at 670 nm. It is also the origin of conical emission formed both in time and frequency domain with the contribution of normal GVD at visible light.