Environmental color affects Nile tilapia reproduction

We investigated the effects of environmental color on the reproductive behavior of Nile tilapia, Oreochromis niloticus. Two environmental colors were tested by covering the aquarium (60 x 60 x 40 cm) with white (12 groups) or blue (13 groups) cellophane and observing reproductive behavior in groups of 2 males (10.27 ± 0.45 cm) and 3 females (10.78 ± 0.45 cm) each. After assignment to the respective environmental color (similar luminosity = 100 to 120 Lux), the animals were observed until reproduction (identified by eggs in the female's mouth) or up to 10 days after the first nest building. Photoperiod was from 6:00 h to 18:00 h every day. Food was offered in excess once a day and water quality was similar among aquaria. Daily observations were made at 8:00, 11:00, 14:00 and 17:00 h regarding: a) latency to the first nest, b) number of nests, c) gravel weight removed (the male excavates the nest in the bottom of the aquarium), d) nest area, and e) mouthbrooding incubation (indication of reproduction). The proportion of reproducing fish was significantly higher (6 of 13) in the group exposed to the blue color compared the group exposed to the white color (1 of 12; Goodman's test of proportions). Moreover, males under blue light removed significantly larger masses of gravel (blue = 310.70 ± 343.50 g > white = 130.38 ± 102.70 g; P = 0.01) and constructed wider nests (blue = 207.93 ± 207.80 cm² > white = 97.68 ± 70.64 cm²; P = 0.03) than the control (white). The other parameters did not differ significantly between light conditions. We concluded that reproduction in the presence of blue light was more frequent and intense than in the presence of white light.

Lämmöntuotannon energiatehokkuuden parantaminen Sotek-säätiön rakennuksissa

Diplomityössä tarkastellaan lämmöntuotannon energiatehokkuuden parantamista neljässä Sotek- säätiön rakennuksessa. Työssä oli tarkoitus selvittää, minkälainen lämmitysjärjestelmä on juuri kyseiseen kiinteistöön järkevin ja investointikustannuksiltaan kannattava. Työssä käydään läpi polttoaineita, lämmöntuotanto- ja lämmönjakotapoja, sekä mietitään kannattaako rakennuksia lisäeristää. Työssä verrataan vanhojen järjestelmien hiilidioksidipäästöjä valittujen uusien järjestelmien hiilidioksidipäästöihin. Kiinteistöjen lämmitys tuottaa Suomessa noin 30 % kaikista hiilidioksidipäästöistä. Se on siis merkittävä alue, josta päästöjä voitaisiin vähentää. Tehtävänä oli laskea kaikille kiinteistöille tarkat lämmitystarpeet ja lämmitystehontarpeet käyttäen apuna Suomen rakennusmääräyskokoelmaa. Työn perusteella lämmöntuotannon energiatehokkuuden parantaminen kohteissa on järkevää ja taloudellisesti kannattavaa muuttamalla lämmöntuotanto pääosin lämpöpumpuille. Täystehoiset järjestelmät eivät tulleet investoinnillisesti kannattavaksi, eikä se ilmalämpöpumpuissa ollut edes mahdollista. Tulosten perusteella lämmitysenergian kustannuksia saatiin vähennettyä parhaiten mitoittamalla kohteisiin osatehoiset lämpöpumput. Lisälämmöneristäminen kohteissa ei taloudellisesti tullut kannattavaksi, vaikka lämmitystarve väheni. Lämmöntuotannon hiilidioksidipäästöt vähenisivät kohteissa keskimäärin noin 50 %.

Tuotteistettu palvelu toimintolaskentajärjestelmän käyttöönottoon

Diplomityön tavoitteena oli kehittää tuotteistettu palvelu toimintolaskentajärjestelmän käyttöönottoon. Käyttöönotolla tarkoitettiin tässä työssä laskennan käyttöönottoa, eli laskentamallin rakentamista toimintolaskentajärjestelmään. Työ tehtiin Solenovo Oy:n toimeksiannosta ja tutkimusmenetelmänä käytettiin toimintatutkimusta. Työ koostuu teoreettisesta viitekehyksestä ja empiirisestä osuudesta. Työn teoreettinen viitekehys muodostuu kolmesta eri aihepiiriä käsittelevästä luvusta. Ensimmäinen käsittelee toimintolaskentaa ja erityisesti sen vahvuuksia, heikkouksia, käyttöönottoa, sekä eroja ja yhtäläisyyksiä verrattuna perinteiseen kustannuslaskentaan. Seuraavana käsitellään palveluita ja niiden kehittämistä. Palvelun kehittämismenetelmistä käsitellään tähän työhön valittu menetelmä service blueprint, sen rakenne ja kehittäminen. Kolmas teoreettisen viitekehyksen osa-alue on palveluiden tuotteistaminen, mikä tarkentui tässä työssä erityisesti asiantuntijapalveluiden tuotteistamiseen. Työn päätuloksena saavutettiin työn tärkein tavoite, eli kehitettiin tuotteistettu palvelu toimintolaskentajärjestelmän käyttöönottoon. Palvelu kehitettiin service blueprint-menetelmää hyödyntäen ja tuotteistettiin soveltuvilta osin. Koska kyseessä oli täysin uusi palvelu, tuotteistaminen painottui tuotteistamisen suunnitteluun ja sisäiseen tuotteistamiseen. Työn aikana määriteltiin palvelun vaatimukset ja sisältö modulointia hyödyntäen, ohjeistus palvelun toteutusta varten, arvioitiin palvelun eri vaiheisiin sisältyviä riskejä ja haasteita, sekä määriteltiin palvelun jatkokehitystarpeet.

Involving employees in six sigma

Six sigma is a quality improvement philosophy with systematic and formal approach. In order to successfully implement and utilize six sigma the basic disciplines of it should be adopted by the entire organization. Furthermore, employee involvement is crucial in six sigma implementation. This thesis addresses the challenges of long-lasting involvement in the case company. It focuses on gaps of involving six sigma trained employees, Black Belts. Theoretical framework of the thesis illustrates different factors influencing employee involvement. Influencing factors can be divided into ten categories: organizational culture, managerial commitment, leadership style, employee empowerment, employees’ perceptions, communication, training, goals, performance measurement and incentives. Factors and categories overlap and are related to each other. The framework provides holistic view of employee involvement in six sigma context but can be used also with other quality management philosophies. This thesis was conducted as a case study and written on an assignment to a power and automation technology company. Due to the nature of research problem, the data collection was conducted by interviewing case company personnel. In order to study involvement from employees’ point of view interview questions were designed to be open-ended and to allow the interviewees to tell freely about the phenomenon. This thesis provides empirical support on previous studies in organizational support, management commitment and employee empowerment. In addition, it indicates the importance of separate function for Black Belts in the organization. The gaps in Black Belt involvement can be categorized under two categories: Management driven gaps are related to management commitment, organizational structure and culture and information systems. Black Belt driven gaps are related to practice and effort of using six sigma. This thesis finds solutions for bridging these gaps in the case company by applying findings from literature research and suggestions given by the interviewees. For each gap, actions are suggested for bridging the discrepancy between current and desired situations. The thesis states that in order to embed six sigma in the organization the most crucial gaps, lack of management commitment, six sigma vision and possibilities to use six sigma, should be diminished.

Taloudellinen kilpailija-analyysi osana strategista johdon laskentatoimea

Tämä kandidaatintutkielma käsittelee asiantuntijaorganisaatioiden tilinpäätöstietojen analysointia taloudellisen kilpailija-analyysin tekniikoita hyödyntäen. Tutkielman tavoitteena oli selvittää, miten kuudessa asiantuntijaorganisaatiossa on pyritty parantamaan tai säilyttämään saavutettu markkina-asema vuosina 2011–2014. Tutkimusmuotona käytettiin tilinpäätösanalyysia. Tutkielma on case-yrityksen toimeksiannosta toteutettu taloudellinen kilpailija-analyysi. Tutkimuksen teoriaosa käsittelee taloudellista kilpailija-analyysia osana strategista johdonlaskentatoimea. Teoreettinen viitekehys rakentuu taloudellisen kilpailija-analyysin tekniikoiden, sekä näitä koskevien empiiristen tutkimusten ympärille. Empiirinen osio jakautui kolmeen osaan, joista kaksi ensimmäistä käsittelivät case-yrityksen määrittelemän yritysjoukon seulomista muutaman taloudellisen tunnusluvun avulla. Varsinainen analyysin painopiste oli kuudelle yritykselle toteutetussa taloudellisessa kilpailija-analyysissa. Teorian pohjalta taloudellisen kilpailija-analyysin tutkimuskohteiksi valittiin kustannusrakenteet, kilpailuasema sekä tilinpäätöstiedot. Tutkielman tarkasteluajanjakso oli mielenkiintoinen, sillä vuosina 2011–2013 liikevaihtojen trendi oli jyrkästi laskeva, mutta vuonna 2014 yleisilme kääntyi nousevaksi. Tarkemman analyysin pohjalta johtopäätöksissä esiin nousivat kasvun ja kannattavuuden tunnusluvut. Opinnäytetyön tutkimustuloksissa havaittiin, että parhaiten tutkimuksen ajanjaksolla liikevaihtojen romahduksesta selvinneillä yrityksillä oli laaja-ansaintapohja sekä joustava kulurakenne. Kannattavuuden parhaiten säilyttäneet yritykset olivat tehneet runsaasti säästöjä henkilöstökuluissa, jotka muodostivat koko aineistossa suurimman osuuden kuluista. Vakavaraisuudeltaan vahvimmat yritykset eivät tehneet rajuja leikkauksia kulurakenteistaan, vaan sietivät muita pidempään heikkoa kannattavuutta.

Helsinki hub – new traffic flows and business networks

This thesis is the Logistics Development Forum's assignment and the work dealing with the development of the Port of Helsinki as part of Helsinki hub. The Forum aims to develop logistics efficiency through public-private co-operation and development of the port is clearly dependent on both factors. Freight volumes in the Port of Helsinki are the biggest single factor in hub and, therefore, the role of the port of the entire hub development is strong. The aim is to look at how the port will develop as a result of changes in the foreign trade of Finland and the Northern European logistics trends in 25 years time period. Work includes the current state analysis and scenario work. The analyses are intended to find out, which trends are the most important in the port volume development. The change and effect of trends is examined through scenarios based on current state. Based on the work, the structure of Finnish export industry and international demand are in the key role in the port volume development. There is significant difference between demands of Finnish exporting products in different export markets and the development between the markets has different impacts on the port volumes by mass and cargo type. On the other hand, the Finnish economy is stuck in a prolonged recession and competition between ports has become a significant factor in the individual port's volume development. Ecological valuesand regulations have changed the competitive landscape and maritime transport emissions reductions has become an important competitive factor for short routes in the Baltic Sea, such as in the link between Helsinki and Tallinn.

Involving employees in six sigma

Six sigma is a quality improvement philosophy with systematic and formal approach. In order to successfully implement and utilize six sigma the basic disciplines of it should be adopted by the entire organization. Furthermore, employee involvement is crucial in six sigma implementation. This thesis addresses the challenges of long-lasting involvement in the case company. It focuses on gaps of involving six sigma trained employees, Black Belts. Theoretical framework of the thesis illustrates different factors influencing employee involvement. Influencing factors can be divided into ten categories: organizational culture, managerial commitment, leadership style, employee empowerment, employees’ perceptions, communication, training, goals, performance measurement and incentives. Factors and categories overlap and are related to each other. The framework provides holistic view of employee involvement in six sigma context but can be used also with other quality management philosophies. This thesis was conducted as a case study and written on an assignment to a power and automation technology company. Due to the nature of research problem, the data collection was conducted by interviewing case company personnel. In order to study involvement from employees’ point of view interview questions were designed to be open-ended and to allow the interviewees to tell freely about the phenomenon. This thesis provides empirical support on previous studies in organizational support, management commitment and employee empowerment. In addition, it indicates the importance of separate function for Black Belts in the organization. The gaps in Black Belt involvement can be categorized under two categories: Management driven gaps are related to management commitment, organizational structure and culture and information systems. Black Belt driven gaps are related to practice and effort of using six sigma. This thesis finds solutions for bridging these gaps in the case company by applying findings from literature research and suggestions given by the interviewees. For each gap, actions are suggested for bridging the discrepancy between current and desired situations. The thesis states that in order to embed six sigma in the organization the most crucial gaps, lack of management commitment, six sigma vision and possibilities to use six sigma, should be diminished.

Onko yrityksen taloudellisella tilalla vaikutusta Tekes-rahoitusta saaneen yrityksen menestymiseen

Tämän tutkielman tavoite on yrityksen tulevan menestymisen tai epäonnistumisen ennustaminen. Tutkimuksen kohteena ovat tutkimus ja kehitys rahoitusta vuosina 2007- 2012 Tekesiltä saaneet mikro- ja pk yritykset. Ennustusta pyrittiin tekemään näille yrityksille niiden rahoitusprojektien alkuhetkeltä (hakemushetki). Tutkimus toteutettiin toimeksiantona Tekesille ja se jatkaa aikaisempaa tutkielmaa, ”Onko projektin henkilöriskitasolla tai talousriskitasolla yhteyttä t&k- projektin onnistumiseen?”. Tämän tutkimuksen johtopäätös oli, ettei varsinkaan talousriskillä ja projektin onnistumisella ole yhteyttä ja sen vuoksi niistä tarvittiin lisää tietoa. Teoreettisessa osuudessa käsitellään yrityksen kasvua ja onnistumisen tai epäonnistumisen ennakointia. Teoria pohjautuu aiheen aikaisempaan kirjallisuuteen ja sen tarkoitus on pohjustaa tutkielmassa tehtyjä valintoja yrityksien menestymisen ennustamiseksi. Tutkimus on toteutettu kvantitatiivisena tutkimuksena. Aineisto koostuu 430 Tekesin t&k- rahoitusta saaneista mikro- ja pk yrityksistä. Empiirisen osuuden tarkoitus oli selvittää, voidaanko koko yrityksen, menestystä ennustaa, jotta rahoitus voidaan kohdistaa paremmin, eli selvittää minkälaisia yrityksiä tulisi rahoittaa, jotta rahoitus kohdistuisi menestyjille. Tämän lisäksi tutkimuksessa haluttiin löytää oikeat muuttujat, joiden avulla yrityksen menestymisen ennustaminen on mahdollista. Menestymisen haluttiin kuvaavan koko yrityksen liiketoiminnan menestymistä. Menestymisen mittariksi valittiin liikevaihdon kasvu ja tarkasteltavaksi ajanjaksoksi aika yrityksen t&k- projektin hakemusvaiheesta, kolmen vuoden päähän projektin päättymisestä. Yritykset jaettiin menestyjiin liikevaihdon kasvun mukaan, ja niistä luotiin neljä koria: “Huiput”, “Kasvut”, “Hiipujat” ja “Konkurssit” ja koreja lähdettiin tutkimaan erilaisten mittarien avulla. Valitut mittarit olivat Tekesin riskiarvio (talousriski, henkilöriski, kehitysriski ja markkinariski), tilinpäätöksen tunnusluvuista kannattavuuden, maksuvalmiuden ja vakavaraisuuden tunnusluvut (liikevoittoprosentti ja sijoitetun pääoman tuottoprosentti, quick ratio ja omavaraisuusaste), projektin omarahoitus (yrityksen hakemusvaiheessa ilmoittama muun rahoituksen lähde, joka voi olla vieraanpääoman ehtoista, oman pääomanehtoista tai tulorahoitusta), sekä muut mittarit (uutuusarvo, jalostusarvo, tuottavuus ja lainojen perimättäjättöhakemukset). Riippumattomuutta testattiin ristiintaulukoinnilla, khiin neliötestillä ja kontingenssikerroin C:n avulla omavaraisuusasteen tunnusluvun osalta yhdistämällä ”Huiput”, ”Kasvut” ja ”Hiipujat” yhteen kotiin ja vertaamalla niitä konkurssiin menneisiin yrityksiin. Lopuksi konkurssiennusteista testattiin pienille yrityksille tarkoitettua Laitisen yhdistelmälukua. Tutkimuksessa havaittiin seuraavaa. Parhaiten yrityksen tulevan kasvun tai konkurssin ennakoivat havainnot seuraavissa muuttujissa: onko hanke rahoitettu lainalla vai avustuksella sekä mikä yrityksen hakemusvaiheen omavaraisuusaste, omarahoitusosuus tai tuottavuus on. Yrityksen hyvä rahatilanne projektin hakemusvaiheessa ei ennusta yrityksen liikevaihdon kasvua. Täydellistä ennustetta kasvulle ei voida tehdä. Laitisen yhdistelmäluku koettiin heikoksi tunnusluvuksi konkurssia ennustettaessa. Tämän takia, sitä muokattiin eri tavoin parhaan mahdollisemman ennusteen saamiseksi. Paras lopputulos saatiin muuttamalla tunnusluvun kriittistä arvoa pienemmäksi.

Improving purchasing process for small purchases at a manufacturing company in chemical industry

This thesis was conducted on assignment by a multinational chemical corporation as a case study. The purpose of this study is to find ways to improve the purchasing process for small purchases at the case company. The improvements looked after are mainly cost and time savings. Purchasing process is the process that starts from the requisition of goods or services and ends when the invoice is paid. In this thesis the purchases with value less than 1000€ are considered to be small. The theoretical framework of the thesis consists of general theoretical view of costs and performance of the purchasing process, different types of purchasing processes and a model for improving purchasing processes. The categorization to small and large purchases is the most important followed by the division between direct and indirect purchases. Also models that provide more strategic perspective for categorization were found to be useful. Auditing and managerial control are important parts of the purchasing process. When considering the transaction costs of purchasing from the costs–benefits perspective large and small purchases should not have the same processes. Purchasing cards, e-procurement and vendor managed inventory are seen as an alternative to the traditional purchasing process. The empirical data collection was done by interviewing the company employees that take part of the purchasing process in their daily work. The interviews had open-ended questions and the answers were coded and analyzed. The results consist of process description and assessment as well as suggestions for potential improvements. At the case company the basic purchasing process was similar to the traditional purchasing process that is entirely done with computers and online. For some categories there was already more sophisticated e-procurement solutions in use. To improve the current e-procurement based solutions elimination of authorization workflow and better information exchange can be seen as potential improvements for most of the case purchases. Purchasing cards and a lightweight form of vendor managed inventory can be seen as potential improvements for some categories. Implementing the changes incurs at least some cost and the benefits might be hard to measure. This thesis has revealed that the small purchases have potential for significant cost and time savings at the case company.

The infared optical properties of Sr2RuO4 and SmTiO3 including an object-oriented resistivity interface /

The perovskite crystal structure is host to many different materials from insulating to superconducting providing a diverse range of intrinsic character and complexity. A better fundamental description of these materials in terms of their electronic, optical and magnetic properties undoubtedly precedes an effective realization of their application potential. SmTiOa, a distorted perovskite has a strongly localized electronic structure and undergoes an antiferromagnetic transition at 50 K in its nominally stoichiometric form. Sr2Ru04 is a layered perovskite superconductor (ie. Tc % 1 K) bearing the same structure as the high-tem|>erature superconductor La2_xSrrCu04. Polarized reflectance measurements were carried out on both of these materials revealing several interesting features in the far-infrared range of the spectrum. In the case of SmTiOa, although insulating, evidence indicates the presence of a finite background optical conductivity. As the temperature is lowered through the ordering temperature a resonance feature appears to narrow and strengthen near 120 cm~^ A nearby phonon mode appears to also couple to this magnetic transition as revealed by a growing asymmetry in the optica] conductivity. Experiments on a doped sample with a greater itinerant character and lower Neel temperature = 40 K also indicate the presence of this strongly temperature dependent mode even at twice the ordering temperature. Although the mode appears to be sensitive to the magnetic transition it is unclear whether a magnon assignment is appropriate. At very least, evidence suggests an interesting interaction between magnetic and electronic excitations. Although Sr2Ru04 is highly anisotropic it is metallic in three-dimensions at low temperatures and reveals its coherent transport in an inter-plane Drude-like component to the highest temperatures measured (ie. 90 K). An extended Drude analysis is used to probe the frequency dependent scattering character revealing a peak in both the mass enhancement and scattering rate near 80 cm~* and 100 cm~* respectively. All of these experimental observations appear relatively consistent with a Fermi-liquid picture of charge transport. To supplement the optical measurements a resistivity station was set up with an event driven object oriented user interface. The program controls a Keithley Current Source, HP Nano-Voltmeter and Switching Unit as well as a LakeShore Temperature Controller in order to obtain a plot of the Resistivity as a function of temperature. The system allows for resistivity measurements ranging from 4 K to 290 K using an external probe or between 0.4 K to 295 K using a Helium - 3 Cryostat. Several materials of known resistivity have confirmed the system to be robust and capable of measuring metallic samples distinguishing features of several fiQ-cm.

The investigation of the reduction mechanism of the 5a-reductase enzyme of Penicillium decumbens /

The 5a-reductase of Penicillium decumbens ATCC 10436 was used as a model for the mammalian enzyme to investigate the mechanism of reduction of testosterone to 5adihydrotestosterone . The purpose of this study was to search for specific 5a-reductase inhibitors which antagonize prostate cancer . In a whole-cell biotransformation mode, this organism reduced testosterone (1) to 5a-dihydrosteroids (8) and 5aandrostane- 3, 17-dione (9) in yields of 28% and 37% respectively. Control experiments have shown that 5aandrostane- 3, 17-dione (9) can be produced from the corresponding alcohol (8) in a subsequent reaction separate from that catalysed by the 5a-reductase enzyme . Androst-4- ene-3, 17-dione (2) is reduced to give only (9) with a recovery of 80% The stereochemistry of the reduction was determined by 500 MHz ^H NMR analysis of the products resulting from the deuterium labelled substrates. The results were obtained by an analysis of the NOE difference spectra, double-quantum filtered phase sensitive COSY 2-D spectra, and ^^c-Ir 2-D shift correlation spectra of deuterium labelled products. According to the unambiguous assignment of the signals due to H-4a and H-4Ii in 5a-dihydro steroids, the NMR data show clearly that addition of hydrogen to the 4{5)K bond has occurred in a trans manner at positions 413 and 5a. To Study the reduction mechanism of this enzyme, several substrates were prepared as following; 3-methyleneandrost-4-en- 17fi-ol(3), androst-4-en-17i5-ol(5) , androst-4-en-3ii, 17fi-diol (6) and 4, 5ii-epoxyandrostane-3, 17-dione (7) . Results suggest that this enzyme system requires an oxygen atom at the 3-position of the steroid in order to bind the substrate. Furthermore, the mechanism of this 5a-reductase may proceed via direct addition of hydrogen at the 4,5 position without involvement of a carbonyl group as an intermediate.

Large amplitude motions in the S1 state of formic acid /

A detailed theoretical investigation of the large amplitude motions in the S, excited electronic state of formic acid (HCOOH) was done. This study focussed on the the S, «- So electronic band system of formic acid (HCOOH). The torsion and wagging large amplitude motions of the S, were considered in detail. The potential surfaces were simulated using RHF/UHF ab-initio calculations for the two electronic states. The energy levels were evaluated by the variational method using free rotor basis functions for the torsional coordinates and harmonic oscillator basis functions for the wagging coordinates. The simulated spectrum was compared to the slit-jet-cooled fluorescence excitation spectrum allowing for the assignment of several vibronic bands. A rotational analysis of certain bands predicted that the individual bands are a mixture of rotational a, b and c-type components.The electronically allowed transition results in the c-type or Franck-Condon band and the electronically forbidden, but vibronically allowed transition creates the a/b-type or Herzberg-Teller components. The inversion splitting between these two band types differs for each band. The analysis was able to predict the ratio of the a, b and c-type components of each band.

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.

Solid state NMR chemical shifts as an alternative to diffraction data in the determination of SIC polytypic structures

Silicon carbide, which has many polytypic modifications of a very simple and very symmetric structure, is an excellent model system for exploring, the relationship between chemical shift, long-range dipolar shielding, and crystal structure in network solids. A simple McConnell equation treatment of bond anisotropy effects in a poly type predicts chemical shifts for silicon and carbon sites which agree well with the experiment, provided that contributions from bonds up to 100 A are included in the calculation. The calculated chemical shifts depend on three factors: the layer stacking sequence, electrical centre of gravity, and the spacings between silicon and carbon layers. The assignment of peaks to lattice sites is proved possible for three polytypes (6H, 15R, and 3C). The fact that the calculated chemical shifts are very sensitive to layer spacings provides us a potential way to detennine and refine a crystal structure. In this work, the layer spacings of 6H SiC have been calculated and are within X-ray standard deviations. Under this premise, the layer spacings of 15R have been detennined. 29Si and 13C single crystal nmr studies of 6H SiC polytype indicate that all silicons and carbons are magnetically anisotropic. The relationship between a magnetic shielding tensor component and layer spacings has been derived. The comparisons between experimental and semi-empirical chemical shielding tensor components indicate that the paramagnetic shielding of silicon should be included in the single crystal chemical shift calculation.

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.