Fluorescence spectra and ab initio theoretical studies of HCOOH /

A fluorescence excitation spectrum of formic acid monomer (HCOOH) , has been recorded in the 278-246 nm region and has been attributed to an n >7r* electron promotion in the anti conformer. The S^< S^ electronic origins of the HCOOH/HCOOD/DCOOH/DCOOD isotopomers were assigned to weak bands observed at 37431.5/37461.5/37445.5/37479.3 cm'''. From a band contour analysis of the 0°^ band of HCOOH, the rotational constants for the excited state were estimated: A'=1.8619, B'=0.4073, and C'=0.3730 cm'\ Four vibrational modes, 1/3(0=0), j/^(0-C=0) , J/g(C-H^^^) and i/,(0-H^yJ were observed in the spectrum. The activity of the antisymmetric aldehyde wagging and hydroxyl torsional modes in forming progressions is central to the analysis, leading to the conclusion that the two hydrogens are distorted from the molecular plane, 0-C=0, in the upper S. state. Ab initio calculations were performed at the 6-3 IG* SCF level using the Gaussian 86 system of programs to aid in the vibrational assignments. The computations show that the potential surface which describes the low frequency OH torsion (twisting motion) and the CH wagging (molecular inversion) motions is complex in the S^ excited electronic state. The OH and CH bonds were calculated to be twisted with respect to the 0-C=0 molecular frame by 63.66 and 4 5.76 degrees, respectively. The calculations predicted the existence of the second (syn) rotamer which is 338 cm'^ above the equilibrium configuration with OH and CH angles displaced from the plane by 47.91 and 41.32 degrees.

Nietzsche's eternal recurrence of the same : the effect of logic abridgement, contradictions and inconsistencies

I will argue that the doctrine of eternal recurrence of the same no better interprets cosmology than pink elephants interpret zoology. I will also argue that the eternal-reiurn-of-the-same doctrine as what Magnus calls "existential imperative" is without possibility of application and thus futile. To facilitate those arguments, the validity of the doctrine of the eternal recurrence of the same will be tested under distinct rubrics. Although each rubric will stand alone, one per chapter, as an evaluation of some specific aspect of eternal recurrence, the rubric sequence has been selected to accommodate the identification of what I shall be calling logic abridgments. The conclusions to be extracted from each rubric are grouped under the heading CONCLUSION and appear immediately following rubric ten. Then, or if, at the end of a rubric a reader is inclined to wonder which rubric or topic is next, and why, the answer can be found at the top of the following page. The question is usually answered in the very first sentence, but always answered in the first paragraph. The first rubric has been placed in order by chronological entitlement in that it deals with the evolution of the idea of eternal recurrence from the time of the ancient Greeks to Nietzsche's August, 1881 inspiration. This much-recommended technique is also known as starting at the beginning. Rubric 1 also deals with 20th. Century philosophers' assessments of the relationship between Nietzsche and ancient Greek thought. The only experience of E-R, Zarathustra's mountain vision, is second only because it sets the scene alluded to in following rubrics. The third rubric explores .ii?.ih T jc,i -I'w Nietzsche's evaluation of rationality so that his thought processes will be understood appropriately. The actual mechanism of E-R is tested in rubric four...The scientific proof Nietzsche assembled in support of E-R is assessed by contemporary philosophers in rubric five. E-R's function as an ethical imperative is debated in rubrics six and seven.. .The extent to which E-R fulfills its purpose in overcoming nihilism is measured against the comfort assured by major world religions in rubric eight. Whether E-R also serves as a redemption for revenge is questioned in rubric nine. Rubric ten assures that E-R refers to return of the identically same and not merely the similar. In addition to assemblage and evaluation of all ten rubrics, at the end of each rubric a brief recapitulation of its principal points concludes the chapter. In this essay I will assess the theoretical conditions under which the doctrine cannot be applicable and will show what contradictions and inconsistencies follow if the doctrine is taken to be operable. Harold Alderman in his book Nietzsche's Gift wrote, the "doctrine of eternal recurrence gives us a problem not in Platonic cosmology, but in Socratic selfreflection." ^ I will illustrate that the recurrence doctrine's cosmogony is unworkable and that if it were workable, it would negate self-reflection on the grounds that selfreflection cannot find its cause in eternal recurrence of the same. Thus, when the cosmology is shown to be impossible, any expected ensuing results or benefits will be rendered also impossible. The so-called "heaviest burden" will be exposed as complex, engrossing "what if speculations deserving no linkings to reality. To identify ^Alderman p. 84 abridgments of logic, contradictions and inconsistencies in Nietzsche's doctrine of eternal recurrence of the same, I. will examine the subject under the following schedule. In Chapter 1 the ancient origins of recurrence theories will be introduced. ..This chapter is intended to establish the boundaries within which the subsequent chapters, except Chapter 10, will be confined. Chapter 2, Zarathustra's vision of E-R, assesses the sections of Thus Spoke Zarathustra in which the phenomenon of recurrence of the same is reported. ..Nihilism as a psychological difficulty is introduced in this rubric, but that subject will be studied in detail in Chapter 8. In Chapter 2 the symbols of eternal recurrence of the same will be considered. Whether the recurrence image should be of a closed ring or as a coil will be of significance in many sections of my essay. I will argue that neither symbolic configuration can accommodate Nietzsche's supposed intention. Chapter 3 defends the description of E-R given by Zarathustra. Chapter 4, the cosmological mechanics of E-R, speculates on the seriousness with which Nietzsche might have intended the doctrine of eternal recurrence to be taken. My essay reports, and then assesses, the argument of those who suppose the doctrine to have been merely exploratory musings by Nietzsche on cosmological hypotheses...The cosmogony of E-R is examined. In Chapter 5, cosmological proofs tested, the proofs for Nietzsche's doctrine of return of the same are evaluated. This chapter features the position taken by Martin ' Heidegger. My essay suggests that while Heidegger's argument that recurrence of the same is a genuine cosmic agenda is admirable, it is not at all persuasive. Chapter 6, E-R is an ethical imperative, is in essence the reporting of a debate between two scholars regarding the possibility of an imperative in the doctrine of recurrence. Their debate polarizes the arguments I intend to develop. Chapter 7, does E-R of the same preclude alteration of attitudes, is a continuation of the debate presented in Chapter 6 with the focus shifted to the psychological from the cosmological aspects of eternal recurrence of the same. Chapter 8, Can E-R Overcome Nihilism?, is divided into two parts. In the first, nihilism as it applies to Nietzsche's theory is discussed. ..In part 2, the broader consequences, sources and definitions of nihilism are outlined. My essay argues that Nietzsche's doctrine is more nihilistic than are the world's major religions. Chapter 9, Is E-R a redemption for revenge?, examines the suggestion extracted from Thus Spoke Zarathustra that the doctrine of eternal recurrence is intended, among other purposes, as a redemption for mankind from the destructiveness of revenge. Chapter 10, E-R of the similar refuted, analyses a position that an element of chance can influence the doctrine of recurrence. This view appears to allow, not for recurrence of the same, but recurrence of the similar. A summary will recount briefly the various significant logic abridgments, contradictions, and inconsistencies associated with Nietzsche's doctrine of eternal recurrence of the same. In the 'conclusion' section of my essay my own opinions and observations will be assembled from the body of the essay.

The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halide molecules /

TITLE: The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halides. AUTHOR: J. L. Brema SUPERVISOR: Dr. D. C. Moule NUMBER OF PAGES: 89 ABSTRACT: The vibrational assignment of the five-in-plane fundamental modes of CSClBr has been made on the basis of infrared gas phase and liquid Raman spectral analyses to supplement our earlier vibrational studies. Even though the one out-of-plane fundamental was not observed spectroscopically an attempt has been made to predict its frequency. The vibrational spectra contained impurity bands and the CSClBr assignment was made only after a thorough analysis of the impurities themselves. A normal co-ordinate analysis calculation was performed assuming a Urey-Bradley force field. This calculation yielded the fundamental frequencies in good agreement with those observed after refinement of the originally transferred force constants. The theoretical frequencies are the eigenvalues of the secular equation and the calculation also gave the corresponding eigenvectors in the form of the very important LLj matrix. The [l] matrix is the transfoirmation between internal co-ordinates and normal co-ordinates and it is essential for Franck-Condon calculations on electronically excited molecules and for infrared Integrated band intensity studies. Using a self-consistent molecular orbital calculation termed "complete neglect of differential overlap" (CNDO/2) , theoretical values of equilibrium bond lengths and angleswere calcuted for a series of carbonyl and thlocarbonyl molecules. From these calculations valence force field force constants were also determined but with limited success. With the CNIX)/2 method theoretical dipole moment derivatives with respect to symmetrized internal co-ordinates were calculated and the results should be useful in a correlation with experimentally determined values.

Optimization of the valence energy variance of the CuH molecule

We developed the concept of split-'t to deal with the large molecules (in terms of the number of electrons and nuclear charge Z). This naturally leads to partitioning the local energy into components due to each electron shell. The minimization of the variation of the valence shell local energy is used to optimize a simple two parameter CuH wave function. Molecular properties (spectroscopic constants and the dipole moment) are calculated for the optimized and nearly optimized wave functions using the Variational Quantum Monte Carlo method. Our best results are comparable to those from the single and double configuration interaction (SDCI) method.

Quantum Monte Carlo : some theoretical and numerical studies

In Part I, theoretical derivations for Variational Monte Carlo calculations are compared with results from a numerical calculation of He; both indicate that minimization of the ratio estimate of Evar , denoted EMC ' provides different optimal variational parameters than does minimization of the variance of E MC • Similar derivations for Diffusion Monte Carlo calculations provide a theoretical justification for empirical observations made by other workers. In Part II, Importance sampling in prolate spheroidal coordinates allows Monte Carlo calculations to be made of E for the vdW molecule var He2' using a simplifying partitioning of the Hamiltonian and both an HF-SCF and an explicitly correlated wavefunction. Improvements are suggested which would permit the extension of the computational precision to the point where an estimate of the interaction energy could be made~

A microanalysis of EMG and EEG changes during the sleep onset period (SOP) : a theoretical investigation with practical applications /

The present study has both theoretical and practical aspects. The theoretical intent of the study was to closely examine the relationship between muscle activity (EMG) and EEG state during the process of falling asleep. Sleep stages during sleep onset (SO) have been generally defined with regards to brain wave activity (Recht schaff en & Kales (1968); and more precisely by Hori, Hayashi, & Morikawa (1994)). However, no previous study has attempted to quantify the changes in muscle activity during this same process. The practical aspect of the study examined the reliability ofa commercially developed wrist-worn alerting device (NovAlert™) that utilizes changes in muscle activity/tension in order to alert its user in the event that he/she experiences reduced wakefulness that may result in dangerous consequences. Twelve female participants (aged 18-42) sp-ent three consecutive nights in the sleep lab ("Adaptation", "EMG", and "NOVA" nights). Each night participants were given 5, twenty-minute nap opportunities. On the EMG night, participants were allowed to fall asleep freely. On the NOV A night, participants wore the Nov Alert™ wrist device that administered a Psychomotor Vigilance Test (PVT) when it detected that muscle activity levels had dropped below baseline. Nap sessions were scored using Hori's 9-stage scoring system (Hori et aI, 1994). Power spectral analyses (FFT) were also performed. Effects ofthe PVT administration on EMG and EEG frequencies were also examined. Both chin and wrist EMG activity showed reliable and significant decline during the early stages ofHori staging (stages HO to H3 characterized by decreases in alpha activity). All frequency bands studied went through significant changes as the participants progressed through each ofHori's 9 SO stages. Delta, theta, and sigma activity increased later in the SO continuum while a clear alpha dominance shift was noted as alpha activity shifted from the posterior regions of the brain (during Hori stages HO to H3) to the anterior portions (during Hori stages H7 to H9). Administration of the PVT produced significant increases in EMG activity and was effective in reversing subjective drowsiness experienced during the later stages of sleep onset. Limitations of the alerting effects of the PVTs were evident following 60 to 75 minutes of use in that PVTs delivered afterwards were no longer able to significantly increase EMG levels. The present study provides a clearer picture of the changes in EMG and EEG during the sleep onset period while testing the efficacy of a commercially developed alerting device. EMG decreases were found to begin during Hori stage 0 when EEG was - dominated by alpha wave activity and were maximal as Hori stages 2 to 5 were traversed (coincident with alpha and beta activity). This signifies that EMG decrements and the loss of resting alpha activity are closely related. Since decreased alpha has long been associated with drowsiness and impending sleep, this investigation links drops in muscle tone with sleepiness more directly than in previous investigations. The EMG changes were reliably demonstrated across participants and the NovAlert™ detected the EMG decrements when Hori stage 3 was entered. The alerting vibrations produced by the NovAlert™ occurred early enough in the SO process to be of practical importance as a sleepiness monitoring and alerting device.

Understanding the Origin of Selectivity in the Asymmetric Lithiation Reaction of N-Heterocycles: A Theoretical Study

The natural abundance of the N-heterocycle containing compounds has pushed the synthetic community toward the invention of new synthetic methods that result in the structural diversity of N-heterocycles. Among this, is the efficient and highly selective diamine mediated asymmetric lithiation process. Amongst the diamine chiral ligands, (-)-sparterine, which is a naturally occurring alkaloid proved to be an efficient one. Many successful, good yielding and highly selective lithiation reactions have been accomplished with the mediation by this chiral diamine base. Although, there are some examples of experimental and theoretical mechanistic studies in the literature, there is a lack of detailed understanding as to how it exactly induces the chirality. In this thesis is described a systematic investigation of how (-)-sparteine influences the stereoselectivity in the course of asymmetric lithiation reaction. This led us to the establishment of the function of A-ring’s β-CH2 effect and D-ring effect. Consequently, the importance of the A-ring and D-ring portions of (-)-sparteine in the stereoselectivity is unraveled. Another part of this thesis deals with the asymmetric lithiation of BF3-activated N,N- dimethylaminoferrocene in the presence of (1R, 2R)-N1,N2-bis(3,3-dimethylbutyl)-N1,N2-dimethylcyclohexane-1,2-diamine ( a (R,R)-TMCDA surrogate) with i-PrLi. Computational findings were in full accord with the experimental observations. Subsequently, the theoretically provided insights into the mechanism of the reaction were exploited in computational design of a new ligand. Unfortunately, the outcome of this design was not experimentally robust and an updated approach towards a successful design was explained.

Spectroscopic and theoretical considerations of cyclopropenone

Please consult the paper edition of this thesis to read. It is available on the 5th Floor of the Library at Call Number: Z 9999 P65 D53 2007

The Effects of Body Posture on Emotion Perception: A Developmental and Theoretical Analysis

Previously, studies investigating emotional face perception - regardless of whether they involved adults or children - presented participants with static photos of faces in isolation. In the natural world, faces are rarely encountered in isolation. In the few studies that have presented faces in context, the perception of emotional facial expressions is altered when paired with an incongruent context. For both adults and 8- year-old children, reaction times increase and accuracy decreases when facial expressions are presented in an incongruent context depicting a similar emotion (e.g., sad face on a fear body) compared to when presented in a congruent context (e.g., sad face on a sad body; Meeren, van Heijnsbergen, & de Gelder, 2005; Mondloch, 2012). This effect is called a congruency effect and does not exist for dissimilar emotions (e.g., happy and sad; Mondloch, 2012). Two models characterize similarity between emotional expressions differently; the emotional seed model bases similarity on physical features, whereas the dimensional model bases similarity on underlying dimensions of valence an . arousal. Study 1 investigated the emergence of an adult-like pattern of congruency effects in pre-school aged children. Using a child-friendly sorting task, we identified the youngest age at which children could accurately sort isolated facial expressions and body postures and then measured whether an incongruent context disrupted the perception of emotional facial expressions. Six-year-old children showed congruency effects for sad/fear but 4-year-old children did not for sad/happy. This pattern of congruency effects is consistent with both models and indicates that an adult-like pattern exists at the youngest age children can reliably sort emotional expressions in isolation. In Study 2, we compared the two models to determine their predictive abilities. The two models make different predictions about the size of congruency effects for three emotions: sad, anger, and fear. The emotional seed model predicts larger congruency effects when sad is paired with either anger or fear compared to when anger and fear are paired with each other. The dimensional model predicts larger congruency effects when anger and fear are paired together compared to when either is paired with sad. In both a speeded and unspeeded task the results failed to support either model, but the pattern of results indicated fearful bodies have a special effect. Fearful bodies reduced accuracy, increased reaction times more than any other posture, and shifted the pattern of errors. To determine whether the results were specific to bodies, we ran the reverse task to determine if faces could disrupt the perception of body postures. This experiment did not produce congruency effects, meaning faces do not influence the perception of body postures. In the final experiment, participants performed a flanker task to determine whether the effect of fearful bodies was specific to faces or whether fearful bodies would also produce a larger effect in an unrelated task in which faces were absent. Reaction times did not differ across trials, meaning fearful bodies' large effect is specific to situations with faces. Collectively, these studies provide novel insights, both developmentally and theoretically, into how emotional faces are perceived in context.