Density-wave theory of dislocations in crystals

The density-wave theory of Ramakrishnan and Yussouff is extended to provide a scheme for describing dislocations and other topological defects in crystals. Quantitative calculations are presented for the order-parameter profiles, the atomic configuration, and the free energy of a screw dislocation with Burgers vector b=(a/2, a/2, a/2) in a bcc solid. These calculations are done using a simple parametrization of the direct correlation function and a gradient expansion. It is conventional to express the free energy of the dislocation in a crystal of size R as (λb2/4π)ln(αR/‖b‖), where λ is the shear elastic constant, and α is a measure of the core energy. Our results yield for Na the value α≃1.94a/(‖c1’’‖)1/2 (≃1.85) at the freezing temperature (371 K) and α≃2.48a/(‖c1’’‖)1/2 at 271 K, where c1’’ is the curvature of the first peak of the direct correlation function c(q). Detailed results for the density distribution in the dislocation, particularly the core region, are also presented. These show that the dislocation core has a columnar character. To our knowledge, this study represents the first calculation of dislocation structure, including the core, within the framework of an order-parameter theory and incorporating thermal effects.

Diagnosis of dominant forcing factors for large-scale vertical velocities during active and break phases of the monsoon

An attempt to diagnose the dominant forcings which drive the large-scale vertical velocities over the monsoon region has been made by computing the forcings like diabatic heating fields,etc. and the large-scale vertical velocities driven by these forcings for the contrasting periods of active and break monsoon situations; in order to understand the rainfall variability associated with them. Computation of diabatic heating fields show us that among different components of diabatic heating it is the convective heating that dominates at mid-tropospheric levels during an active monsoon period; whereas it is the sensible heating at the surface that is important during a break period. From vertical velocity calculations we infer that the prime differences in the large-scale vertical velocities seen throughout the depth of the atmosphere are due to the differences in the orders of convective heating; the maximum rate of latent heating being more than 10 degrees Kelvin per day during an active monsoon period; whereas during a break monsoon period it is of the order of 2 degrees Kelvin per day at mid-tropospheric levels. At low levels of the atmosphere, computations show that there is large-scale ascent occurring over a large spatial region, driven only by the dynamic forcing associated with vorticity and temperature advection during an active monsoon period. However, during a break monsoon period such large-scale spatial organization in rising motion is not seen. It is speculated that these differences in the low-level large-scale ascent might be causing differences in convective heating because the weaker the low level ascent, the lesser the convective instability which produces deep cumulus clouds and hence lesser the associated latent heat release. The forcings due to other components of diabatic heating, namely, the sensible heating and long wave radiative cooling do not influence the large-scale vertical velocities significantly.

Molecular structure-activity relationship study of some non-steroidal antiinflammatory agents using electrostatic potential mapping

A series of 6,11-dihydro-11-oxodibenz[b,e]oxepin-2-acetic acids (DOAA) which are known to be anti-inflammatory agents were studied. The geometries of some of the molecules obtained from X-ray crystallography were used in the calculations as such while the geometries of their derivatives were obtained by local, partial geometry optimization around the Sites of substitution employing the AMI method, keeping the remaining parts of the geometries the same as those in the parent molecules. Molecular electrostatic potential (MEP) mapping was performed for the molecules using optimized hybridization displacement charges (HDC) combined with Lowdin charges, as this charge distribution has been shown earlier to yield near ab initio quality results. A good correlation has been found between the MEP values near the oxygen atoms of the hydroxyl groups of the carboxy groups of the molecules and their anti-inflammatory activities. The result is broadly in agreement with the model proposed earlier by other authors regarding the structure-activity relationship for other similar molecules.

Electronic structure of square planar CuO46− clusters

The results of spin-polarized MSXagr calculations show that the ground state of the CuO 4 6– cluster is essentially non-magnetic in spite of odd number of electrons in the system for short Cu–O distances (1.90 Å) as found in the highT c superconductors. This arises due to the fact that the unpaired electron resides in a molecular orbital with primarily oxygen 3s character. The stability of this molecular orbital is found to be sensitive to the cluster geometry and thus, increase in Cu–O distance (as well as other changes affecting oxygen-oxygen distance) tend to favour a magnetic state. From these calculations we have also estimated the Coulomb correlation strength within the Cu 3d to be about 5.3 eV.

Cognitive Functioning in Alcohol and Other Substance Use Disorders in Young Adulthood : A Genetic Epidemiological Study

Alcohol and other substance use disorders (SUDs) result in great costs and suffering for individuals and families and constitute a notable public health burden. A multitude of factors, ranging from biological to societal, are associated with elevated risk of SUDs, but at the level of individuals, one of the best predictors is a family history of SUDs. Genetically informative twin and family studies have consistently indicated this familial risk to be mainly genetic. In addition, behavioral and temperamental factors such as early initiation of substance use and aggressiveness are associated with the development of SUDs. These familial, behavioral and temperamental risk factors often co-occur, but their relative importance is not well known. People with SUDs have also been found to differ from healthy controls in various domains of cognitive functioning, with poorer verbal ability being among the most consistent findings. However, representative population-based samples have rarely been used in neuropsychological studies of SUDs. In addition, both SUDs and cognitive abilities are influenced by genetic factors, but whether the co-variation of these traits might be partly explained by overlapping genetic influences has not been studied. Problematic substance use also often co-occurs with low educational level, but it is not known whether these outcomes share part of their underlying genetic influences. In addition, educational level may moderate the genetic etiology of alcohol problems, but gene-environment interactions between these phenomena have also not been widely studied. The incidence of SUDs peaks in young adulthood rendering epidemiological studies in this age group informative. This thesis investigated cognitive functioning and other correlates of SUDs in young adulthood in two representative population-based samples of young Finnish adults, one of which consisted of monozygotic and dizygotic twin pairs enabling genetically informative analyses. Using data from the population-based Mental Health in Early Adulthood in Finland (MEAF) study (n=605), the lifetime prevalence of DSM-IV any substance dependence or abuse among persons aged 21—35 years was found to be approximately 14%, with a majority of the diagnoses being alcohol use disorders. Several correlates representing the domains of behavioral and affective factors, parental factors, early initiation of substance use, and educational factors were individually associated with SUDs. The associations between behavioral and affective factors (attention or behavior problems at school, aggression, anxiousness) and SUDs were found to be largely independent of factors from other domains, whereas daily smoking and low education were still associated with SUDs after adjustment for behavioral and affective factors. Using a wide array of neuropsychological tests in the MEAF sample and in a subsample (n=602) of the population-based FinnTwin16 (FT16) study, consistent evidence of poorer verbal cognitive ability related to SUDs was found. In addition, participants with SUDs performed worse than those without disorders in a task assessing psychomotor processing speed in the MEAF sample, whereas no evidence of more specific cognitive deficits was found in either sample. Biometrical structural equation models of the twin data suggested that both alcohol problems and verbal ability had moderate heritabilities (0.54—0.72), and that their covariation could be explained by correlated genetic influences (genetic correlations -0.20 to -0.31). The relationship between educational level and alcohol problems, studied in the full epidemiological FT16 sample (n=4,858), was found to reflect both genetic correlation and gene-environment interaction. The co-occurrence of low education and alcohol problems was influenced by overlapping genetic factors. In addition, higher educational level was associated with increased relative importance of genetic influences on alcohol problems, whereas environmental influences played a more important role in young adults with lower education. In conclusion, SUDs, especially alcohol abuse and dependence, are common among young Finnish adults. Behavioral and affective factors are robustly related to SUDs independently of many other factors, and compared to healthy peers, young adults who have had SUDs during their life exhibit significantly poorer verbal cognitive ability, and possibly less efficient psychomotor processing. Genetic differences between individuals explain a notable proportion of individual differences in risk of alcohol dependence, verbal ability, and educational level, and the co-occurrence of alcohol problems with poorer verbal cognition and low education is influenced by shared genetic backgrounds. Finally, various environmental factors related to educational level in young adulthood moderate the relative importance of genetic factors influencing the risk of alcohol problems, possibly reflecting differences in social control mechanisms related to educational level.

Hormones andCuscuta development: In vitro induction of haustoria by cytokinin and its inhibition by other hormones

Cytokinins induced haustoria formation in excised 10-mm segments ofCuscuta vine, the subapical 25-to-50-mm region being most responsive, producing a mean of 4–6 haustoria per segment. The order of effectiveness of cytokinins continuously applied (72 h) was 6-benzylaminopurine (BA) ges isopentenyladenine (iP) Gt zeatin (Z). Ribosides of BA and Z were as effective as the bases, whereas riboside of iP ([9R]iP) was half as effective as iP. Haustoria induction was influenced by weather and seasonal conditions at the time of vine collection; materials obtained on warm, sunny days responded better than those obtained on rainy, cloudy, or cool days. Haustoria were induced equally well all around the segment, and no thigmostimulus was needed for induction. p ]A 10-min pulse of 100 mgrM BA induced half as many haustoria as a 60-min pulse or continuous application of BA. White light inhibited haustoria induction elicited by a short (30-min) pulse of BA, whereas a longer (120-min) BA application overcame this light inhibition. Auxins (IAA or NAA, 1–10 mgrM), gibberellin (GA3, 1–10 mgrM), ethylene (as ethrel, 10–100 mgrM), and abscisic acid (ABA, 100 mgrM) were individually inhibitory (60–80%) with respect to haustoria induction when given continuously with 50 mgrM BA. A 60-min pulse of auxins (10 mgrM), GA3 (100 mgrM), or ethrel (10 mgrM), given at various time intervals during or after a 60-min pulse of 100 mgrM BA, showed that inhibition was maximal (70–95%) between 4 and 16 h of BA application and negligible (GA3) or much reduced (auxin, ethrel) at 20 h, indicating a ldquocommitmentrdquo to haustoria formation by this time.

Functional limitations and quality of life in schizophrenia and other psychotic disorders

There is substantial evidence of the decreased functional capacity, especially everyday functioning, of people with psychotic disorder in clinical settings, but little research about it in the general population. The aim of the present study was to provide information on the magnitude of functional capacity problems in persons with psychotic disorder compared with the general population. It estimated the prevalence and severity of limitations in vision, mobility, everyday functioning and quality of life of persons with psychotic disorder in the Finnish population and determined the factors affecting them. This study is based on the Health 2000 Survey, which is a nationally representative survey of 8028 Finns aged 30 and older. The psychotic diagnoses of the participants were assessed in the Psychoses of Finland survey, a substudy of Health 2000. The everyday functioning of people with schizophrenia is studied widely, but one important factor, mobility has been neglected. Persons with schizophrenia and other non-affective psychotic disorders, but not affective psychoses had a significantly increased risk of having both self-reported and test-based mobility limitations as well as weak handgrip strength. Schizophrenia was associated independently with mobility limitations even after controlling for lifestyle-related factors and chronic medical conditions. Another significant factor associated with problems in everyday functioning in participants with schizophrenia was reduced visual acuity. Their vision was examined significantly less often during the five years before the visual acuity measurement than the general population. In general, persons with schizophrenia and other non-affective psychotic disorder had significantly more limitations in everyday functioning, deficits in verbal fluency and in memory than the general population. More severe negative symptoms, depression, older age, verbal memory deficits, worse expressive speech and reduced distance vision were associated with limitations in everyday functioning. Of all the psychotic disorders, schizoaffective disorder was associated with the largest losses of quality of life, and bipolar I disorder with equal or smaller losses than schizophrenia. However, the subjective loss of qualify of life associated with psychotic disorders may be smaller than objective disability, which warrants attention. Depressive symptoms were the most important determinant of poor quality of life in all psychotic disorders. In conclusion, subjects with psychotic disorders need regular somatic health monitoring. Also, health care workers should evaluate the overall quality of life and depression of subjects with psychotic disorders in order to provide them with the basic necessities of life.

Hila- ja kuviotason laskennan vaikutus kuvion kokonaistilavuuteen, tallennustilaan ja laskentaaikaan teoreettista läpimittajakaumaa ja runkolukusarjaa käyttämällä

Metsäsuunnittelussa tarvittavan metsävaratiedon keräämisessä ollaan Suomessa siirtymässä kuvioittaisesta arvioinnista laserkeilaus- ja ilmakuvapohjaiseen kaukokartoitukseen. Tämän tutkimuksen tarkoitus oli selvittää kuvion kokonaistilavuuden ja läpimittajakauman ennustamisen tarkkuus koealan metsikkö- ja puustotunnuksista MSN-, PRM-, ML- ja FMM-menetelmiä sekä Weibull-jakaumaa hyödyntäen seuraavilla tavoilla: 1. PRM-menetelmällä hilatasolla, 2. PRMmenetelmällä kuviotasolla, 3. ML-menetelmällä hilatasolla ja 4. ML-menetelmällä kuviotasolla. Lisäksi kuvion kokonaistilavuuden ennustamisen tarkkuus selvitettiin hyödyntäen kuviolle tuotettua runkolukusarjaa. Tulokset laskettiin puulajikohtaisesti männylle, kuuselle, koivulle ja muille puulajeille. Puulajien tulokset laskettiin kuviotasolla yhteen. Lisäksi selvitettiin menetelmien laskenta-ajan ja tallennustilan tarve. Tutkimuksen aineistona käytettiin Hämeen ammattikorkeakoulun Evon toimipisteen metsistä mitattuja kiinteäsäteisiä ympyräkoealoja, joita oli 249 kappaletta. Hakkuukoneella mitattiin 12kuvion, joiden pinta-alat vaihtelivat välillä 0,2 – 1,94 hehtaaria, puustotiedot. Aluepohjaisen laserkeilausaineiston pulssin tiheys oli 1,8/m2 ja ilmakuvien pikselikoko 0,5 metriä. Kuvion kokonaistilavuus ennustettiin tai estimoitiin laserkeilaus- ja ilmakuva-aineiston piirteiden avulla koealojen puustotunnuksista. Tulokset laskettiin erikseen kaikille kuvioille ja kuvioille, joiden pinta-ala oli yli 0,5 hehtaaria. Yli 0,5 hehtaarin kuvioita oli 8 kappaletta. Kuvion hilojen naapureina käytettiin 1 - 10 koealaa. Menetelmästä ja naapurien määrästä riippuen kokonaistilavuuden suhteellinen RMSE ja harha vaihtelivat välillä 20,76 – 52,86 prosenttia ja -12,04 – 46,54 prosenttia. Vastaavat luvut yli 0,5 hehtaarin kuvioilla olivat 6,74 – 59,41 prosenttia ja -8,04 – 49,59 prosenttia. Laskenta-aika vaihteli menetelmien ja käytettyjen naapurien määrän mukaan voimakkaasti. Kehittyneemmällä ohjelmoinnilla ja ohjelmistolla laskenta-ajat voivat laskea merkittävästi. Tallennustila ei testatuilla menetelmillä ole rajoittava tekijä laajassakaan mittakaavassa. Läpimittajakauman perusteella PRM-menetelmä ennustaa puulajille erittäin kapean läpimittajakauman, jos koeala koostuu vain muutamasta lähes samankokoisesta puusta. Tämä vaikutti tuloksiin erityisesti menetelmällä PRM2.

Conformational analysis of the right-hand twisted antiparallel β-Structure

The conformational analysis of a pair of two-linked peptide units in the anti-parallel arrangement is reported here with a view to study the effect of association of one chain with the other. The pair of two-linked peptide units were fixed in space through the hydrogen bonds between them, in accordance with certain hydrogen bond criteria. Model building was undertaken to ascertain whether the proximity of the side-chains could be used to eliminate any one of the right-hand twisted, left-hand twisted or regular β-structures. Stereochemically, it was found possible with all of them. The preference for a right-hand twisted β-structure, however, was indicated by the classical energy calculations. The relevance of the results thus obtained is discussed in the context of the preferential right-hand twist of the β-pleated sheets present in globular proteins. The agreement between the minimum energy conformations obtained for the pair of two-linked peptide units and the globular protein data is also indicated.

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

Topological defects in crystals: A density-wave theory

A new approach for describing dislocations and other topological defects in crystals, based on the density wave theory of Ramakrishnan and Yussouff is presented. Quantitative calculations are discussed in brief for the order parameter profiles, the atomic configuration and the free energy of a screw dislocation with Burgers vector b = (a/2, a/2,a/2 ) in a bcc solid. Our results for the free energy of the dislocation in a crystal of sizeR, when expressed as (λb 2/4π) ln (αR/|b|) whereλ is the shear elastic constant, yield, for example, the valueα ⋍ 1·85 for sodium at its freezing temperature (371°K). The density distribution in the presence of the dislocation shows that the dislocation core has a columnar character. To our knowledge, this study represents the first calculation of dislocation structure, including the core, within the framework of an order parameter theory incorporating thermal effects.

Magnetically induced currents and magnetic response properties of molecules

The magnetically induced currents in organic monoring and multiring molecules, in Möbius shaped molecules and in inorganic all-metal molecules have been investigated by means of the Gauge-including magnetically induced currents (GIMIC) method. With the GIMIC method, the ring-current strengths and the ring-current density distributions can be calculated. For open-shell molecules, also the spin current can be obtained. The ring-current pathways and ring-current strengths can be used to understand the magnetic resonance properties of the molecules, to indirectly identify the effect of non-bonded interactions on NMR chemical shifts, to design new molecules with tailored properties and to discuss molecular aromaticity. In the thesis, the magnetic criterion for aromaticity has been adopted. According to this, a molecule which has a net diatropic ring current might be aromatic. Similarly, a molecule which has a net paratropic current might be antiaromatic. If the net current is zero, the molecule is nonaromatic. The electronic structure of the investigated molecules has been resolved by quantum chemical methods. The magnetically induced currents have been calculated with the GIMIC method at the density-functional theory (DFT) level, as well as at the self-consistent field Hartree-Fock (SCF-HF), at the Møller-Plesset perturbation theory of the second order (MP2) and at the coupled-cluster singles and doubles (CCSD) levels of theory. For closed-shell molecules, accurate ring-current strengths can be obtained with a reasonable computational cost at the DFT level and with rather small basis sets. For open-shell molecules, it is shown that correlated methods such as MP2 and CCSD might be needed to obtain reliable charge and spin currents. The basis set convergence has to be checked for open-shell molecules by performing calculations with large enough basis sets. The results discussed in the thesis have been published in eight papers. In addition, some previously unpublished results on the ring currents in the endohedral fullerene Sc3C2@C80 and in coronene are presented. It is shown that dynamical effects should be taken into account when modelling magnetic resonance parameters of endohedral metallofullerenes such as Sc3C2@C80. The ring-current strengths in a series of nano-sized hydrocarbon rings are related to static polarizabilities and to H-1 nuclear magnetic resonance (NMR) shieldings. In a case study on the possible aromaticity of a Möbius-shaped [16]annulene we found that, according to the magnetic criterion, the molecule is nonaromatic. The applicability of the GIMIC method to assign the aromatic character of molecules was confirmed in a study on the ring currents in simple monocylic aromatic, homoaromatic, antiaromatic, and nonaromatic hydrocarbons. Case studies on nanorings, hexaphyrins and [n]cycloparaphenylenes show that explicit calculations are needed to unravel the ring-current delocalization pathways in complex multiring molecules. The open-shell implementation of GIMIC was applied in studies on the charge currents and the spin currents in single-ring and bi-ring molecules with open shells. The aromaticity predictions that are made based on the GIMIC results are compared to other aromaticity criteria such as H-1 NMR shieldings and shifts, electric polarizabilities, bond-length alternation, as well as to predictions provided by the traditional Hückel (4n+2) rule and its more recent extensions that account for Möbius twisted molecules and for molecules with open shells.