The electronic spectra and the determination of the excited state geometry of 3A" propynal /|nby Chhiu-Tsu Lin. -- 260 St. Catharines, Ont. : [s. n.],

Impurity free eluission spectra of HCCCHO and DCCCHO have been rephotographed using the electronic-energy-exchange method with benzene as a carrier gas. The near ultraviolet spectra of ReeCHO and DCCCHO were photographed in a sorption under conditions of high resolution with absorption path lengths up to 100 meters. The emission and absorption spectra of Propynal resulting from 3 n 1 t 1\ - A excitation has been reanalyzed in som.e detail. Botrl of the eH out-of-plane wagging modes were found to have negative anharmonicity. A barrier height of 56.8/0.0 cm- 1 and a nonplanar oft , , equilibrium angle of 17 3 /30 are calculated for the V 10/ lJ 11 modes. The in-plane and out-of-plane v1. brational modes in the 3A." and 1a~. ' elec ronic states of Propynal were subjected to a normal coordinate treatment in the approximat :on of tIle Urey-Bradley force field. From the relative oscillator strengths of the trans1·t1·0ns connect i ng t he v ibrat1•0n1ess lA' , state and t,he V1· bron1·C 3· if levels of the A state, the differences in equilibrium configuration were evaluated from an approximate Franck-Condon analysis based on the ground state normal coordinates. As this treatment gave 512 possible geometrical structures for the upper state, it 4 was necessary to resort to a comparison of the observed and calculated moments of inertia along with chemical intuition to isolate the structure. A test of the correctness of the calculated structure change and the vibrational assignment was raade by evaluating the intensities of the inplane and out-oi-plane fundarnental, sequence, and cross sequellce transitions y the exact Franck-Condon method.

Some concepts and models usefulninthe analysis of discrete life time data

This thesis entitled Reliability Modelling and Analysis in Discrete time Some Concepts and Models Useful in the Analysis of discrete life time data.The present study consists of five chapters. In Chapter II we take up the derivation of some general results useful in reliability modelling that involves two component mixtures. Expression for the failure rate, mean residual life and second moment of residual life of the mixture distributions in terms of the corresponding quantities in the component distributions are investigated. Some applications of these results are also pointed out. The role of the geometric,Waring and negative hypergeometric distributions as models of life lengths in the discrete time domain has been discussed already. While describing various reliability characteristics, it was found that they can be often considered as a class. The applicability of these models in single populations naturally extends to the case of populations composed of sub-populations making mixtures of these distributions worth investigating. Accordingly the general properties, various reliability characteristics and characterizations of these models are discussed in chapter III. Inference of parameters in mixture distribution is usually a difficult problem because the mass function of the mixture is a linear function of the component masses that makes manipulation of the likelihood equations, leastsquare function etc and the resulting computations.very difficult. We show that one of our characterizations help in inferring the parameters of the geometric mixture without involving computational hazards. As mentioned in the review of results in the previous sections, partial moments were not studied extensively in literature especially in the case of discrete distributions. Chapters IV and V deal with descending and ascending partial factorial moments. Apart from studying their properties, we prove characterizations of distributions by functional forms of partial moments and establish recurrence relations between successive moments for some well known families. It is further demonstrated that partial moments are equally efficient and convenient compared to many of the conventional tools to resolve practical problems in reliability modelling and analysis. The study concludes by indicating some new problems that surfaced during the course of the present investigation which could be the subject for a future work in this area.

Some bivariate life time models in discrete time"

The term reliability of an equipment or device is often meant to indicate the probability that it carries out the functions expected of it adequately or without failure and within specified performance limits at a given age for a desired mission time when put to use under the designated application and operating environmental stress. A broad classification of the approaches employed in relation to reliability studies can be made as probabilistic and deterministic, where the main interest in the former is to device tools and methods to identify the random mechanism governing the failure process through a proper statistical frame work, while the latter addresses the question of finding the causes of failure and steps to reduce individual failures thereby enhancing reliability. In the probabilistic attitude to which the present study subscribes to, the concept of life distribution, a mathematical idealisation that describes the failure times, is fundamental and a basic question a reliability analyst has to settle is the form of the life distribution. It is for no other reason that a major share of the literature on the mathematical theory of reliability is focussed on methods of arriving at reasonable models of failure times and in showing the failure patterns that induce such models. The application of the methodology of life time distributions is not confined to the assesment of endurance of equipments and systems only, but ranges over a wide variety of scientific investigations where the word life time may not refer to the length of life in the literal sense, but can be concieved in its most general form as a non-negative random variable. Thus the tools developed in connection with modelling life time data have found applications in other areas of research such as actuarial science, engineering, biomedical sciences, economics, extreme value theory etc.

Ground and Excited State Electron Transfer Reaction Between a few Anthracene Appended Tertiary Amines and Suitable Electron Acceptors

the thesis entitled “Ground and Excited State Electron Transfer Reaction Between a few Anthracene Appended Tertiary Amines and Suitable Electron Acceptors” portrays our attempts to explore the solvent, concentration and temperature effect of the reaction between a few (anthracen-9- yl)methanamines with electron acceptors like DMAD, DBA and DBE. We have also studied the effect of solvent and percentage fluorescence quenching in the photoinduced electron transfer reactions of these ‘donor-spacer-acceptor’ systems. Finally we look in to the intramolecular electron transfer reactions of a few tertiary amine appended dibenzobarrelenes and bisdibenzobarrelenes

Basis set superposition error effects, excited-state potential energy surface and photodynamics of thymine

En aquesta tesi he estudiat l'efecte de l'error de superposició de base (BSSE) en la planaritat d'algunes molècules. He observat que l'ús d'alguns mètodes de càlcul amb determinades funcions de base descriuen mínims d'energia no planars per les bases nitrogenades de l'ADN. He demostrat que aquests problemes es poden arreglar utilitzant el mètode Counterpoise per corregir el BSSE en els càlculs. En aquesta tesi també he estudiat la fotofísica de la timina i els resultats mostren que existeixen dos camins de relaxació des de l'estat excitat que permeten la regeneració de l'estructura inicial de forma ultraràpida.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297

Excited state electronic polarization and reappraisal of the n <- pi* emission of acetone in water

Electronic polarization of the acetone molecule in the excited n -> pi* state is considered and its influence on the solvent shift in the emission spectrum is analyzed. Using an iterative procedure the electronic polarizations of both the ground and the excited states are included and compared with previous results obtained with Car-Parrinello dynamics. Analysis of the emission transition obtained using CIS(D)/aug-cc-pVDZ on statistically uncorrelated solute-solvent structures, composed of acetone and twelve explicit water molecules embedded in the electrostatic field of remaining 263 water molecules, corroborates that the solvent effect is mild, calculated here between 80 and 380 cm (1). (c) 2010 Published by Elsevier B.V.

Excited-state absorption spectroscopy in oxidized Cytochrome c

This work reports on the excited-state absorption spectrum of oxidized Cytochrome c (Fe(3+)) dissolved in water, measured with the Z-scan technique with femtosecond laser pulses. The excited-state absorption cross-sections between 460 and 560 nm were determined with the aid of a three-energy-level model. Reverse saturable absorption was observed below 520 nm, while a saturable absorption process occurs in the Q-band, located around 530 nm. Above 560 nm, a competition between saturable absorption and two-photon absorption was inferred. These results show that Cytochrome c presents distinct nonlinear behaviors, which may be useful to study electron transfer chemistry in proteins by one- and two-photon absorption. In addition, owing to these nonlinear optical features, this molecule may be employed in applications involving photodynamics therapy and saturable absorbers. (C) 2009 Elsevier B.V. All rights reserved.

Excited State Absorption of Doped and Undoped Polyanyline

Polyaniline is a conducting polymer with appealing electrical and optical properties, arising from the -conjugation along the polymer backbone. The understanding of its excited state absorption is of prime importance for designing and fabricating optical devices. Here, we report on the study of the excited state absorption of doped and undoped PANI by using femtosecond pulses in the spectral range from 450nm up to 850nm. For undoped PANI, we observed saturation of absorption as well as reverse saturable absorption, depending on the excitation wavelength. For doped PANI, however, only saturable absorption was observed.

Excited-state dynamics of polyfluorene derivatives in solution

The excited-state dynamics of two polyfluorene copolymers, one fully conjugated containing phenylene vinylene units alternated with 9,9`-dihexylfluorenyl groups and the other segmented by -(CH2)(8)- spacer, were studied in dilute solution of different solvents using a picosecond single-photon timing technique. The excited-state dynamics of the segmented copolymer follows the Forster resonant energy-transfer model which describes intrachain energy-transfer kinetics among random oriented chromophores. Energy transfer is confirmed by analysis of fluorescence anisotropy relaxation with the measurement of a short decay component of about 60 ps. The fluorescence decay surface of the fully conjugated copolymer is biexponential with decay times of about 470 and 900 ps, ascribed to deactivation of chain moieties containing trans and cis isomers already in a photostationary condition. Thus, energy transfer is very fast due to the conjugated nature and rigid-rod-like structure of this copolymer chain.

Prediction of a weakly bound excited state in the He-4(2)-Li-7 molecule

A scale-independent approach, valid for weakly bound three-body systems, is used to analyze the existence of excited Thomas-Efimov states in molecular systems with three atoms: a helium dimer together with isotopes of lithium (Li-6 and Li-7) and sodium (Na-23). With the present study and the available data, we can clearly predict that the He-4(2)-Li-7 system supports an excited state with binding energy close to 2.31 mK. (C) 2000 American Institute of Physics. [S0021-9606(00)30442-1].

Electron transfer by singlet excited state of porphyn and electron acceptor affinity in rigid medium: photoacoustic phase angle analysis

A espectroscopia fotoacústica obtém informações sobre amplitude e fase, da resposta de um sistema submetido a excitação por luz. Este artigo apresenta estudos do ângulo de fase no processo de transfereência de elétrons entre octaetilporfirina (OEP) e derivados de quinona ambos dispersos em uma matriz polimérica. Observou-se uma tendência no comportamento da fase para valores menores na região espectral próximo de 620 nm. Enquanto que para comprimentos de onda menores este efeito não foi apresentado. Estas medidas sugerem que a transferência de elétrons para o aceitador ocorreu com a participação do estado singleto excitado da octaetilporfirina.