Time-Resolved Resonance Raman Spectroscopic Studies on the Triplet Excited State of Thioxanthone

Thioxanthone has been investigated extensively owing to its unique photochemical and photophysical applications and its solvatochromic behavior. Here, we report the time-resolved resonance Raman studies on the structure of the lowest triplet excited state of thioxanthone in carbon tetrachloride. In addition, FT-IR and FT-Raman techniques have been used to study the vibrational structure in the ground state. To corroborate the experimental findings, density functional theory calculations have been carried out. Isotopic calculations and normal coordinate analysis have been used to help in assigning the observed bands to Raman vibrational modes. Structural information derived from this study is expected to help in better understanding the triplet state photochemistry of thioxanthone.

A Neuro-Adaptive Approach for Robust Control of High Performance Aircrafts with Parameter Inaccuracies

For high performance aircrafts, the flight control system needs to be quite effective in both assuring accurate tracking of pilot commands, while simultaneously assuring overall stability of the aircraft. In addition, the control system must also be sufficiently robust to cater to possible parameter variations. The primary aim of this paper is to enhance the robustness of the controller for a HPA using neuro-adaptive control design. Here the architecture employs a network of Gaussian Radial basis functions to adaptively compensate for the ignored system dynamics. A stable weight mechanism is determined using Lyapunov theory. The network construction and performance of the resulting controller are illustrated through simulations with a low-fidelity six –DOF model of F16 that is available in open literature.

Continuous-time Single Network Adaptive Critic for Regulator Design of Nonlinear Control Affine Systems

An optimal control law for a general nonlinear system can be obtained by solving Hamilton-Jacobi-Bellman equation. However, it is difficult to obtain an analytical solution of this equation even for a moderately complex system. In this paper, we propose a continuoustime single network adaptive critic scheme for nonlinear control affine systems where the optimal cost-to-go function is approximated using a parametric positive semi-definite function. Unlike earlier approaches, a continuous-time weight update law is derived from the HJB equation. The stability of the system is analysed during the evolution of weights using Lyapunov theory. The effectiveness of the scheme is demonstrated through simulation examples.

Convergence problems in a class of model reference adaptive control systems

A class of model reference adaptive control system which make use of an augmented error signal has been introduced by Monopoli. Convergence problems in this attractive class of systems have been investigated in this paper using concepts from hyperstability theory. It is shown that the condition on the linear part of the system has to be stronger than the one given earlier. A boundedness condition on the input to the linear part of the system has been taken into account in the analysis - this condition appears to have been missed in the previous applications of hyperstability theory. Sufficient conditions for the convergence of the adaptive gain to the desired value are also given.

Scattering theory and linear optimal control: Regulator and servo problems

In this paper, several known computational solutions are readily obtained in a very natural way for the linear regulator, fixed end-point and servo-mechanism problems using a certain frame-work from scattering theory. The relationships between the solutions to the linear regulator problem with different terminal costs and the interplay between the forward and backward equations have enabled a concise derivation of the partitioned equations, the forward-backward equations, and Chandrasekhar equations for the problem. These methods have been extended to the fixed end-point, servo, and tracking problems.

Analysis and design of machine foundations at resonance

The design of machine foundations are done on the basis of two principal criteria viz., vibration amplitude should be within the permissible limits and natural frequency of machine-foundation-soil system should be away from the operating frequency (i.e. avoidance of resonance condition). In this paper the nondimensional amplitude factor M-m or M-r m and the nondimensional frequency factor a(o m) at resonance are related using elastic half space theory and is used as a new approach for a simplified design procedure for the design of machine foundations for all the modes of vibration fiz. vertical, horizontal, rocking and torsional for rigid base pressure distribution and weighted average displacement condition. The analysis show that one need not know the value of Poisson's ratio for rotating mass system for all the modes of vibration.

Simultaneous Detection of Two Triplets: A Time-Resolved Resonance Raman Study

Solvents are known to affect the triplet state structure and reactivity. In this paper, we have employed time-resolved resonance Raman (TR3) spectroscopy to understand solvent-induced subtle structural changes in the lowest excited triplet state of thioxanthone. Density functional theory (DFT) combined with the self-consistent reaction field (SCRF) implicit solvation model has been used to calculate the vibrational frequencies in the solvents. Here, we report a unique observation of the coexistence of two triplets, which has been substantiated by the probe wavelength-dependent Raman experiments. The coexistence of two triplets has been further supported by photoreduction experiments carried out at various temperatures.

Effect of chlorine substitution on triplet state structure of thioxanthone: A time-resolved resonance Raman study

Substitution plays an important role in determining the triplet state reactivity. In this paper, we have studied the effect of chlorine substitution on the triplet state structure and the reactivity of thioxanthone (TX). We have employed time-resolved resonance Raman technique to understand the structure of the lowest triplet excited state of 2-chlorothioxanthone (CTX). The experimental findings have been corroborated with the computational results using density functional theory. Akin to the parent compound (TX), coexistence of two lowest triplet states has been observed in case of CTX, which has been substantiated using resonant probe wavelength dependence study. The relative contribution of 3n-pi* to 3 pi-pi* to the equilibrated triplet state has been found to be more for CTX compared to TX suggesting increase in the triplet state reactivity after the substitution. The above observation has been further supported by the flash photolysis experiments. Copyright (C) 2013 John Wiley & Sons, Ltd.

Stochastic analysis of epidemics on adaptive time varying networks

Many studies investigating the effect of human social connectivity structures (networks) and human behavioral adaptations on the spread of infectious diseases have assumed either a static connectivity structure or a network which adapts itself in response to the epidemic (adaptive networks). However, human social connections are inherently dynamic or time varying. Furthermore, the spread of many infectious diseases occur on a time scale comparable to the time scale of the evolving network structure. Here we aim to quantify the effect of human behavioral adaptations on the spread of asymptomatic infectious diseases on time varying networks. We perform a full stochastic analysis using a continuous time Markov chain approach for calculating the outbreak probability, mean epidemic duration, epidemic reemergence probability, etc. Additionally, we use mean-field theory for calculating epidemic thresholds. Theoretical predictions are verified using extensive simulations. Our studies have uncovered the existence of an ``adaptive threshold,'' i.e., when the ratio of susceptibility (or infectivity) rate to recovery rate is below the threshold value, adaptive behavior can prevent the epidemic. However, if it is above the threshold, no amount of behavioral adaptations can prevent the epidemic. Our analyses suggest that the interaction patterns of the infected population play a major role in sustaining the epidemic. Our results have implications on epidemic containment policies, as awareness campaigns and human behavioral responses can be effective only if the interaction levels of the infected populace are kept in check.

Adaptive selection of search space in look ahead orthogonal matching pursuit

Compressive Sensing theory combines the signal sampling and compression for sparse signals resulting in reduction in sampling rate and computational complexity of the measurement system. In recent years, many recovery algorithms were proposed to reconstruct the signal efficiently. Look Ahead OMP (LAOMP) is a recently proposed method which uses a look ahead strategy and performs significantly better than other greedy methods. In this paper, we propose a modification to the LAOMP algorithm to choose the look ahead parameter L adaptively, thus reducing the complexity of the algorithm, without compromising on the performance. The performance of the algorithm is evaluated through Monte Carlo simulations.

Feshbach resonance in a synthetic non-Abelian gauge field

We study the Feshbach resonance of spin-1/2 particles in a uniform synthetic non-Abelian gauge field that produces spin-orbit coupling and constant spin potentials. We develop a renormalizable quantum field theory including the closed-channel boson which engenders the resonance. We show that the gauge field shifts the Feshbach field where the low-energy scattering length diverges. In addition the Feshbach field is shown to depend on the center-of-mass momentum of the particles. For high-symmetry gauge fields which produce a Rashba spin coupling, we show that the system supports two bound states over a regime of magnetic fields when the background scattering length is negative and the resonance width is comparable to the energy scale of the spin-orbit coupling. We discuss interesting consequences useful for future theoretical and experimental studies, even while our predictions are in agreement with recent experiments.

Single network adaptive critic aided dynamic inversion for optimal regulation and command tracking with online adaptation for enhanced robustness

To combine the advantages of both stability and optimality-based designs, a single network adaptive critic (SNAC) aided nonlinear dynamic inversion approach is presented in this paper. Here, the gains of a dynamic inversion controller are selected in such a way that the resulting controller behaves very close to a pre-synthesized SNAC controller in the output regulation sense. Because SNAC is based on optimal control theory, it makes the dynamic inversion controller operate nearly optimal. More important, it retains the two major benefits of dynamic inversion, namely (i) a closed-form expression of the controller and (ii) easy scalability to command tracking applications without knowing the reference commands a priori. An extended architecture is also presented in this paper that adapts online to system modeling and inversion errors, as well as reduced control effectiveness, thereby leading to enhanced robustness. The strengths of this hybrid method of applying SNAC to optimize an nonlinear dynamic inversion controller is demonstrated by considering a benchmark problem in robotics, that is, a two-link robotic manipulator system. Copyright (C) 2013 John Wiley & Sons, Ltd.

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.