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Riigieelarveliste ressursside võimalused on piiratud, mistõttu tuleb otsida tõhusamaid võimalusi siseturvalisuse tagamiseks. Siseturvalisuse organisatsioonide jaoks on kõige tavapärasemaks sündmuseks, kuhu reageerivad nii politsei-, kiirabi- kui päästeressurss, liiklusõnnetus, kuhu operatiivressursid teevad aastas enam kui 10 000 väljasõitu. Liiklusõnnetused tähendavad ühiskonnale suuri kulutusi, mille mõju ulatub kannatanute isiklikust kahjust riigi majanduseni. Ehkki Eesti avalik sektor on kõrgelt digitaliseeritud, koguvad paraku erinevad riigiasutused rohkelt andmeid vaid oma organisatsiooni esmaste seaduses ettenähtud ülesannete täitmiseks. Kasutades läbimõeldumalt juba kogutud andmeid, võivad need pakkuda olulist lisaväärtust. Selleks uuriti käesolevas magistritöös, kuidas rasked ilmastikutingimused ja riiklikud pühad avaldavad mõju liiklusõnnetuste toimumisele eesmärgiga planeerida edaspidi tõhusamalt operatiivressursside tegevust ning seeläbi ennetada ohte ja vähendada liiklusõnnetuste tagajärjel tekkivat kahju. Hüpoteese testiti kahe lineaarse regressioonimudeliga andmetöötlusprogrammis RStudio. Tulemustest selgus, et liiklusõnnetusi toimus pigem enam elanikerohkemates piirkondades ning vähem riiklikel pühadel ja neile järgnevatel päevadel. Rasketest ilmastikutingimustest tingituna toimus liiklusõnnetusi rohkem temperatuuril alla -15˚C ja jäite korral, kuid vähem pimedal ajal. Kannatanuga liiklusõnnetusi toimus samuti enam elanikerohkemates piirkondades. Riiklikud pühad ja neile järgnevad päevad kannatanuga liiklusõnnetuste toimumist ei mõjutanud. Raskete ilmastikutingimuste korral ei toimunud oluliselt enam kannatanuga liiklusõnnetusi. Vaid õhuniiskuse tõustes toimus sagedamini kannatanuga liiklusõnnetusi. Omakorda pimedal ajal toimus kannatanuga liiklusõnnetusi harvem. Kuigi mõlemad töös esitatud mudelid osutusid statistiliselt oluliseks, tuleks nii riskide prognoosimisel kui ka operatiivressursside tegevuste planeerimisel kasutada esimest mudelit, mis uuris kõiki liiklusõnnetusi ning mille tunnuste vahel oli keskmise tugevusega seos. Kuna liiklusõnnetuste toimumise ning raskete ilmastikutingimuste, riiklike pühade ja piirkonna elanike arvu vahel olid statistiliselt olulised seosed, tuleks uute andmete lisandumisel analüüsidega jätkata ning kaaluda mudeli täiendamist uute tunnustega., http://www.ester.ee/record=b4641540*est

The present white paper presents five principles that can guide the design and implementation of effective and appropriate approaches to e-coaching and discusses both their scientific underpinnings and their (potential) applications. The paper crystallises insights that have emerged in recent and ongoing research developed in the Healthy Lifestyle Solutions programme, which is co-ordinated by the Technology Foundation STW and jointly funded by Philips Research and NWO’s National Initiative for Brain and Cognition (NIHC). Those research projects are focused on the areas of diet, exercise, sleep, and stress, but their applications are even wider.

The present white paper presents five principles that can guide the design and implementation of effective and appropriate approaches to e-coaching and discusses both their scientific underpinnings and their (potential) applications. The paper crystallises insights that have emerged in recent and ongoing research developed in the Healthy Lifestyle Solutions programme, which is co-ordinated by the Technology Foundation STW and jointly funded by Philips Research and NWO’s National Initiative for Brain and Cognition (NIHC). Those research projects are focused on the areas of diet, exercise, sleep, and stress, but their applications are even wider.

In the present work, we study the vibrational spectrum of ammonia in full dimensionality (6D), with special emphasis on the tunneling splitting. The inversion motion, i.e., the active mode v(2), is indeed relatively well decoupled from the other five inactive modes. Therefore, an adiabatic separation in an active wave function and an inactive one, approximated with a 5D-harmonic basis function, is certainly well adapted to describing this motion. This separation leads to several 1D-effective Hamiltonians for each 5D-harmonic basis function or adiabatic channel. Two models have been tested: the harmonic adiabatic approximation (HADA), when only one channel is used and the coupled HADA (cHADA), when several channels are coupled. In order to get reliable values for tunneling splitting, our calculations have shown that: (i) the calculation of the electronic potential has to be performed with a large atomic basis set (up to quintuple zeta) with a method including core-valence correlation; (ii) the cHADA is required since the HADA overestimates the energy levels. Furthermore, our values for the tunneling splitting are in good agreement with the experimental data of ammonia and several isotopomers. (C) 2004 Elsevier B.V. All rights reserved.

When studying an N-particle system by means of N-1 vectors i.e., by means of a vector parametrization, one unavoidably comes across several angular momenta: not only the total angular momentum of the system but also the various partial angular momenta corresponding to the motion of the various vectors. All these momenta can, in addition, be referred to a variety of reference frames. The use of vector parametrizations and partial angular momenta in physics greatly simplifies the classical as well as quantum expressions of the kinetic energy. The present paper is devoted to a detailed and rigorous study of the partial angular momenta and the various commutation relations they satisfy, in particular the unusual commutation relations whose origin is traced back to the very structure of the coordinate changes used to define the Body-Fixed (BF) frames. The direct quantization of the classical expressions of the kinetic energy obtained in the context of various vector parametrizations is also given in detail. It turns out to be an efficient extension of well-known quantization procedures to the case where supernumerary quasi-momenta are used. As an illustration, the case of a four-particle system is treated in detail for a particular choice of the BF frames. Finally, the analogies between the classical and quantum approaches are emphasized. (C) 2003 Elsevier B.V. All rights reserved.

Common duckweed (Lemna minor L.) is ideally suited to test the impact of metals on freshwater vascular plants. Literature on cadmium (Cd) and uranium (U) oxidative responses in L. minor are sparse or, for U, non-existent. It was hypothesised that both metals impose concentration-dependent oxidative stress and growth retardation on L. minor. Using a standardised 7-day growth inhibition test, the adverse impact of these metals on L. minor growth was confirmed, with EC50 values for Cd and U of 24.1 2.8 and 29.5 1.9 lM, respectively, and EC10 values of 1.5 0.2 and 6.5 0.9 lM, respectively. The metal-induced oxidative stress response was compared through assessing the activity of different antioxidative enzymes [catalase, glutathione reductase, superoxide dismutase (SOD), ascorbate peroxidase (APOD), guaiacol peroxidase (GPOD) and syringaldizyne peroxidase (SPOD)]. Significant changes in almost all antioxidative enzymes indicated their importance in counteracting the U- and Cd-imposed oxidative burden. However, some striking differences were also observed. For activity of APODs and SODs, a biphasic but opposite response at low Cd compared to U concentrations was found. In addition, Cd (0.520 lM) strongly enhanced plant GPOD activity, whereas U inhibited it. Finally, in contrast to Cd, U up to 10 lM increased the level of chlorophyll a and b and carotenoids. In conclusion, although U and Cd induce similar growth arrest in L. minor, the U-induced oxidative stress responses, studied here for the first time, differ greatly from those of Cd.

Contains fulltext : 143201.pdf (Publisher’s version ) (Open Access) Radboud Universiteit Nijmegen, 17 maart 2015 Promotor : Wigboldus, D.H.J. Co-promotor : Langner, O. 173 p.

Quantum dynamical approaches based on product-grids are limited to the studies of molecular systems with few degrees of freedom, typically less than ten. Recently, Avila et al. [G. Avila, T. Carrington, J. Chem. Phys., 131 (2009) 174103] have introduced the Smolyak scheme [S.A. Smolyak, Sov. Math. Dokl., 4 (1963) 240], which considerably reduces the size of the grids. This approach has pushed back the present calculation limits on the vibrational spectra of polyatomic molecules. In the present study, we have developed an extension of the standard Smolyak scheme in which this scheme is combined with multidimensional grids, such as cubatures, to obtain new sparse grids. This scheme has been applied to the study of the torsional energy levels of methanol in full dimensionality (12D).

The harmonic adiabatic approximation (HADA), an efficient and accurate quantum method to calculate highly excited vibrational levels of molecular systems, is presented. It is well-suited to applications to "floppy molecules" with a rather large number of atoms (N >3). A clever choice of internal coordinates naturally suggests their separation into active, slow, or large amplitude coordinates q('), and inactive, fast, or small amplitude coordinates q('), which leads to an adiabatic (or Born-Oppenheimer-type) approximation (ADA), i.e., the total wave function is expressed as a product of active and inactive total wave functions. However, within the framework of the ADA, potential energy data concerning the inactive coordinates q(') are required. To reduce this need, a minimum energy domain (MED) is defined by minimizing the potential energy surface (PES) for each value of the active variables q('), and a quadratic or harmonic expansion of the PES, based on the MED, is used (MED harmonic potential). In other words, the overall picture is that of a harmonic valley about the MED. In the case of only one active variable, we have a minimum energy path (MEP) and a MEP harmonic potential. The combination of the MED harmonic potential and the adiabatic approximation (harmonic adiabatic approximation: HADA) greatly reduces the size of the numerical computations, so that rather large molecules can be studied. In the present article however, the HADA is applied to our benchmark molecule HCN/CNH, to test the validity of the method. Thus, the HADA vibrational energy levels are compared and are in excellent agreement with the ADA calculations (adiabatic approximation with the full PES) of Light and Bacic [J. Chem. Phys. 87, 4008 (1987)]. Furthermore, the exact harmonic results (exact calculations without the adiabatic approximation but with the MEP harmonic potential) are compared to the exact calculations (without any sort of approximation). In addition, we compare the densities of the bending motion during the HCN/CNH isomerization, computed with the HADA and the exact wave function. (C) 2001 American Institute of Physics.

Within the framework of an adequate spectral representation, the geometrical description of an N-atom molecular system by n = N - 1 Jacobi relative position vectors is shown to be particularly advantageous with regard to the criterion of prediagonalization of the matrix representing the kinetic energy operator. (C) 1998 American Institute of Physics, [S0021-9606(98)02121-7]

It is shown that the geometrical description of a three-atom molecular system by two Jacobi relative position vectors is, within the framework of an adequate representation, particularly advantageous with regard to the criterion of maximal pre-diagonalization of the matrix representing the kinetic energy operator. (C) 1998 Elsevier Science B.V.

Asch’s seminal research on “Forming Impressions of Personality” (1946) has widely been cited as providing evidence for a primacy-of-warmth effect, suggesting that warmth-related judgments have a stronger influence on impressions of personality than competence-related judgments (e.g., Fiske, Cuddy, & Glick, 2007; Wojciszke, 2005). Because this effect does not fit with Asch’s Gestalt-view on impression formation and does not readily follow from the data presented in his original paper, the goal of the present study was to critically examine and replicate the studies of Asch’s paper that are most relevant to the primacy-of-warmth effect. We found no evidence for a primacy-of-warmth effect. Instead, the role of warmth was highly context-dependent, and competence was at least as important in shaping impressions as warmth. (PsycINFO Database Record (c) 2014 APA, all rights reserved). (journal abstract)

After elimination of the centre of mass translation, a vector parametrization for an N-atom molecular system, consisting of N-1 relative position vectors, is used. Sets of 3N-6 local coordinates well suited for describing the system are introduced: they are all made up of the N-1 vector lengths, N-2 planar angles of vector pairs and N-3 dihedral angles for vector triplets. In addition, three Euler angles describe the orientation of the body-fixed frame: the first two angles allow one to orient the z-BF axis, either parallel to one vector or perpendicular to the plane of two vectors; the third angle is for rotation around z, completing the link between the molecule (i.e. the vectors) and the BF axes. The three Euler angles, together with the 3N-6 local coordinates, make up a set of N-1 triplets of spherical coordinates for the relative position vectors, with respect to various frames. This property is used to derive exact expressions of general quantum mechanical kinetic energy operators, and also to propose a polyspherical-harmonics representation in which the kinetic energy matrix may take a relatively simple form (i.e. prediagonalized to a large extent). (C) 1997 Elsevier Science B.V.

Whereas model constraints (e.g., frozen bonds, rigidified atomic groups, etc.) are often resorted to for the calculation of the potential energy surfaces of polyatomic molecules, the derivation of exact expressions for the corresponding kinetic energy operators is a rather new topic. Indeed, the dimensions of the configuration spaces being altered, the differential operators should be modified accordingly, but not the multiplicative operators. In addition, the physical condition J = 0 (where J is the total angular momentum vector) which, from a mathematical viewpoint, is a set of three constraints, also is often considered. The particular question raised is: in the derivation of the kinetic energy operator, is the order in which we apply the model constraints on the one hand and the dynamic constraints J = 0 on the other hand, immaterial? The answer is yes.

Whereas model constraints (namely, internal degrees of freedom either frozen or stepwise adjusted by gradient methods) are often imposed for calculating the potential energies of polyatomic molecules by quantum-chemical methods, the derivation of exact expressions for the corresponding kinetic energy operators is difficult because of the changes of metrics of the configuration spaces, which modify the differential operators but not the multiplicative operators. An appropriate method for overcoming this difficulty has been designed in the case of rigid constraints (e.g., frozen groups) (M. Menou and X. Chapuisat, J. Mel. Spectrosc. 159, 300-328, 1993). In this article, it is generalized to the case of adiabatic constraints; i.e., the variations of certain internal degrees of freedom are adjusted to those of other degrees of freedom. Exact kinetic energy operators are derived. An example is analyzed. (C) 1997 Academic Press.

We present new techniques for an automatic computation of the kinetic energy operator in analytical form. These techniques are based on the use of the polyspherical approach and are extended to take into account Cartesian coordinates as well. An automatic procedure is developed where analytical expressions are obtained by symbolic calculations. This procedure is a full generalization of the one presented in Ndong et al., [J. Chem. Phys. 136, 034107 (2012)]. The correctness of the new implementation is analyzed by comparison with results obtained from the TNUM program. We give several illustrations that could be useful for users of the code. In particular, we discuss some cyclic compounds which are important in photochemistry. Among others, we show that choosing a well-adapted parameterization and decomposition into subsystems can allow one to avoid singularities in the kinetic energy operator. We also discuss a relation between polyspherical and Z-matrix coordinates: this comparison could be helpful for building an interface between the new code and a quantum chemistry package.

As the environment is inevitably exposed to ionizing radiation from natural and anthropogenic sources, it is important to evaluate gamma radiation induced stress responses in plants. The objective of this research is therefore to investigate radiation effects in Arabidopsis thaliana on individual and subcellular level by exposing 2-weeks-old seedlings for 7 days to total doses of 3.9 Gy, 6.7 Gy, 14.8 Gy and 58.8 Gy and evaluating growth, photosynthesis, chlorophyll a, chlorophyll b and carotenoid concentrations and antioxidative enzyme capacities. While the capacity of photosystem II (PSII measured as Fv/Fm) remained intact, plants started optimizing their photosynthetic process at the lower radiation doses by increasing the PSII efficiency (φPSII) and the maximal electron transport rate (ETRmax) and by decreasing the non-photochemical quenching (NPQ). At the highest radiation dose, photosynthetic parameters resembled those of control conditions. On subcellular level, roots showed increased superoxide dismutase (SOD) and ascorbate peroxidase (APX) capacities under gamma irradiation but catalase (CAT), syringaldazine peroxidase (SPX) and guaiacol peroxidase (GPX) activities, on the other hand, decreased. In the leaves no alterations were observed in SOD, CAT and SPX capacities, but GPX was highly affected. Based on these results it seems that roots are more sensitive for oxidative stress under gamma radiation exposure than leaves.

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article i nfo Backlash effect Sex discrimination Gender stereotype Gender prejudice System justification theory Impression management Agentic female leaders risk social and economic penalties for behaving counter-stereotypically (i.e., backlash; Rudman, 1998), but what motivates prejudice against female leaders? The status incongruity hypothesis (SIH) proposes that agentic women are penalized for status violations because doing so defends the gender hierarchy. Consistent with this view, Study 1 found that women are proscribed from dominant, high status displays (which are reserved for leaders and men); Studies 2-3 revealed that prejudice against agentic fe- male leaders was mediated by a dominance penalty; and in Study 3, participants' gender system-justifying beliefs moderated backlash effects. Study 4 found that backlash was exacerbated when perceivers were primed with a system threat. Study 5 showed that only female leaders who threatened the status quo suf- fered sabotage. In concert, support for the SIH suggests that backlash functions to preserve male dominance by reinforcing a double standard for power and control.

The description of the dynamics of polyatomic molecules provides a significant challenge to molecular theorists. For floppy molecular systems the use of curvilinear coordinates (z-matrix, polyspherical...) enables one to perform the dynamics more efficiently. The complexity of the kinetic energy operator is hidden behind a numerical and exact description using TNUM. Furthermore, for molecules with a large number of atoms, the number of internal degrees of freedom makes the reduction of dimensionality a requirement that cannot be ignored. Several physical models of increasing accurateness based on a separation between n slow degrees of freedom (active modes) and m fast ones (inactive modes) can be used (constraint models, adiabatic approximation, coupled adiabatic channels or exact models). All those models are implemented in the fortran code ELVIBROT without built-in limitation. This program allows simulations of vibrational spectra of floppy molecular systems (methanol, ammonia...) as well as time-dependant simulations (photo-dissociation, optimal control ...).

It is shown that, along a reaction path defined as a line in an atomic Cartesian component configuration space (whatever the actual definition of this line, provided that it joins continuously the reagent and the product representative points through all intermediate stationary points), overall (i.e. tumbling) rotation of the body-fixed frame of reference linked with the molecular system (the only relevant definition of 'molecular rotation' for a very deformable molecular system) necessarily takes place, a point generally overlooked and even sometimes denied.

In this study we investigate miscommunications in interactions between human pilots and a virtual wingman, represented by our virtual agent Ashley. We made an inventory of the type of problems that occur in such interactions using recordings of Ashley in flight briefings with pilots and designed a perception experiment to find evidence of human pilots providing cues on the occurrence of miscommunications. In this experiment, stimuli taken from the recordings are rated by naive participants on successfulness. Results show the largest part of miscommunications concern floor management. Participants are able to correctly assess the success of interactions, thus indicating cues for such judgment are present, though successful interactions are better recognized. Moreover, we see stimulus modality (audio, visual or combined) does not influence the ability of participants to judge the success of the interactions. From these results, we present recommendations for further developing virtual wingmen. © 2011 Springer-Verlag.

The angular momentum operator math of a particle obeys the usual commutation rule math×math = iℏmath. In contrast, the total angular momentum operator math of a set of particles relative to moving axes (as, for instance, when mounted on a tumbling molecule) obeys the anomalous commutation rule math×math = −iℏmath. We give a pedagogical and mathematically nonsophisticated description of intermediate cases for which partial angular momentum operators, relative to various moving frames, obey unusual commutation relations that are neither usual nor anomalous. Insight into the origin of these unusual commutation relations provides a means of guessing the type of commutation rule that will be obeyed. In particular, it gives a way to avoid, as far as possible, the unusual commutation relations, which lead to complicated and nonsystematic expressions. Some examples from molecular physics are presented.

The internal rotation (nu(9)) of nitric acid is studied using several ab initio models including 1D models and full dimensionality (9D) ones. For the 9D calculations, an adiabatic separation between the large amplitude motion, i.e. the torsion, and the eight other modes is performed. The potential energy surface is calculated at CCSD(T) level with a triple zeta atomic basis set and is expanded in a Taylor series up to the second-order along the torsional path. The vibrational calculations are performed with the codes ElVibRot and Tnum. Our main results show that the torsional energy levels and the corresponding tunneling spliting are in good agreement with the experimental ones. Furthermore, the resonance between 2nu(9) and nu(5) (NO(2) in-plane bending) is also well described with full dimensionality models.

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In a recent paper (Molec. Phys. 1991, 73, 1183), Bramley et al. analysed the physical and mathematical context in which the vibrational rotational Hamiltonian operator for a molecule is expressed in terms of Euler angles for the rotation and internal curvilinear coordinates for the vibration. In the case of a generic tetra-atomic molecule, they derived a few rules which determine the choice of the basis functions, in order (i) to ensure continuity and single-valuedness of the eigenfunctions and (ii) to cancel out the singularities (infinite integrals) that unavoidably crop up in the matrix representation of the vibration-rotation kinetic energy operator. In another recent paper (Phys. Rev. A, 1992, 45, 6217), Chapuisat and lung considered the vibration-rotation of a polyatomic molecule as resulting from the rotational-vibrational motion of coupled relative vectors; with the help of a standard representation for the angular motion of each vector viewed in the moving frame resulting from the first two Euler rotations, i.e. for the whole molecule a direct product of spherical harmonics, they have shown that it is possible to get rid of the singularities and to derive, after completing the third Euler rotation, analytical expressions of the kinetic energy operator matrix elements in the usual bending-torsion-rotation basis. In implementing this approach, the rules derived for tetra-atomics by Bramley et al. are confirmed and are next generalized to the case of the N-atom molecule. The restrictions to the direct product representation which must be explicitly taken into account are established on the basis of a purely physical analysis of the coupled vector motion.

Contains fulltext : 77079.pdf (author's version ) (Open Access)

After a brief review of the basic algebraic ingredients needed to express the quantum-mechanical Hamiltonian of an /b N/-body system in terms of curvilinear coordinates and quasi-momentum operators, the effect of changing the normalization convention is thoroughly investigated, with special emphasis on the occurrence of a nondifferential term in the expression of the kinetic energy operator, the so-called `extrapotential' term. Four examples are presented, concerning various parametrizations and various referentials, for acetylene-like molecules.