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 In addition, some previously unpublished results on the ring currents in the endohedral fullerene Sc3C2@C80 and in coronene are presented.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.

Khα1,2 hypersatellites of 3d transition metals and their photoexcitation energy dependence

Hollow atoms in which the K shell is empty while the outer shells are populated allow studying a variety of important and unusual properties of atoms. The diagram x-ray emission lines of such atoms, the K-h alpha(1,2) hypersatellites (HSs), were measured for the 3d transition metals, Z=23-30, with a high energy resolution using photoexcitation by monochromatized synchrotron radiation. Good agreement with ab initio relativistic multiconfigurational Dirac-Fock calculations was found. The measured HS intensity variation with the excitation energy yields accurate values for the excitation thresholds, excludes contributions from shake-up processes, and indicates domination near threshold of a nonshake process. The Z variation of the HS shifts from the diagram line K alpha(1,2), the K-h alpha(1)-K-h alpha(2) splitting, and the K-h alpha(1)/K-h alpha(2) intensity ratio, derived from the measurements, are also discussed with a particular emphasis on the QED corrections and Breit interaction.

Microsite occupancy and spatial structure of regeneration in three late-successional Norway spruce forests in northern Europe

A comparison of microsite occupancy and the spatial structure of regeneration in three areas of late-successional Norway spruce dominated forest. Pallas-Ylläs is understood to have been influenced only by small-scale disturbance; Dvina-Pinega has had sporadic larger-scale disturbances; Kazkim has been affected by fire. All spruce and birch trees with diameter at breast height (DBH) ?10 cm were mapped in five stands on 40 m x 400 m transects, and those with DBH < 10 cm on 2 or 4 m x 400 m subplots. Microsite type was inventoried at 1m intervals along the centre line and for each tree with DBH < 10 cm. At all study areas small seedlings (h < 0.3 m, DBH < 10 cm) preferentially occupied disturbed microsites. In contrast, spruce saplings (h ? 1.3 m, DBH <10 cm) at all study areas showed less, or no, preference. At Pallas-Ylläs spruce seedlings (h < 1.3 m, DBH < 10 cm) and saplings (h ? 1.3 m, DBH < 10 cm) exhibited spatial correlation at scales from 32-52 m. At Dvina-Pinega saplings of both spruce and birch exhibited spatial correlation at scales from 32-81 m. At Kazkim spatial correlation of seedlings and saplings of both species was exhibited over variable distances. No spatial cross-correlation was found between overstorey basal area (DBH ? 10 cm) and regeneration (h ? 1.3 m, DBH < 10 cm) at any study area. The results confirm the importance of disturbed microsites for seedling establishment, but suggest that undisturbed microsites may sometimes be more advantageous for long-term tree survival. The regeneration gap concept may not be useful in describing the regeneration dynamics of late-successional boreal forests.

Concentrations and loads of some metals and fluorine in the River Kokemäenjoki in 1975 and 1977

Tiivistelmä: Metallien ja fluorin pitoisuuksista ja määristä Kokemäenjoessa vuosina 1975—1977

The Commercial Structure of Pedestrian Streets and Shopping Districts - Three Cases from Finland

Kävelykadut ovat tunnustettu tapa elävöittää keskusta-alueiden kauppaa. Aluksi moni kauppias epäilee kävelykadun tuomia muutoksia, mutta kokemus osoittaa, että kävelykadut ovat olleet menestyksekkäitä ja nostavat siellä olevien yritysten myyntiä. Jotkut yritykset eivät kuitenkin hyödy kävelykaduista, kun taas toiset hyötyvät paljon kun katu muuttuu kävelykaduksi. Tämä pro gradu -tutkielma tutkii kävelykatujen kaupallista rakennetta, jotta saataisiin selville minkätyyppiset yritykset löytyvät kävelykadulta. Tuloksia verrataan sen kaupallisen keskusvyöhykkeen kaupalliseen rakenteeseen missä kävelykatu sijaitsee. Näin saadaan selville erot kaupallisessa rakenteessa. Pro gradu tutkii myös miten tavallisia ketjuyritykset ovat kävelykaduilla ja kaupallisissa keskusvyöhykkeissä. Tutkimusaineisto koottiin kaupallisen inventoinnin avulla, joka suoritettiin kolmessa suomalaisessa kaupungissa: Tammisaaressa, Keravalla ja Porissa. Saatu aineisto luokiteltiin ja tulokset piirrettiin kartalle. Perustilastollisia menetelmiä käytettiin tulosten analysoimisessa. Tulokset eriteltiin kävelykadun, kauppakeskusten ja muiden paikkojen osalta ja luokiteltiin yleisluokkiin vähittäiskauppa, ravintola ja muu palvelu. Tulokset näyttävät, että on olemassa selkeitä eroja kun vertaa kävelykatuja ja kaupallisia keskusvyöhykkeitä. Kävelykaduilla on paljon enemmän vähittäiskauppoja, etenkin muotikauppoja, kuin muilla kaduilla. Kauppakeskuksilla on samantapainen kaupallinen rakenne kuin kävelykaduilla kun taas muilla kaduilla esiintyy vähemmän vähittäiskauppoja ja enemmän palveluyrityksiä. Ravintolat ovat melkein yhtä tavallisia koko kaupallisessa keskusvyöhykkeessä. Ketjuyritysten osalta tulokset ovat epäselviä. On olemassa osviittaa siitä, että ne ovat tavallisempia kävelykaduilla, etenkin suurissa kaupungeissa. Saatua tulosta ei ole kuitenkin tarpeeksi, jotta varmaa tietoa olisi saatu. Viimeisten 10–15 vuoden ajan Suomen kävelykadut ovat muuttuneet enemmän ravintolavaltaisiksi muiden palveluiden kustannuksella. Vähittäiskauppojen määrä on pysynyt vakaana. Suomalaiset kävelykadut eroavat kaupalliselta rakenteeltaan pohjoismaisista kävelykaduista, joilla on enemmän vähittäiskauppoja ja vähemmän palveluyrityksiä. Tapauskohtaisissa tuloksissa esiintyy paljon eroavaisuuksia. Paikalliset tekijät ovat usein voimakkaampia kuin yleiset teoriat kauppojen sijainnista kävelykaduilla. Yleisesti ottaen tulokset tukevat teoreettista viitekehystä. Tulokset antavat tarkempaa tietoa kävelykatujen ja kaupallisten keskusvyöhykkeiden kaupallisesta rakenteesta ja siitä, mitkä tekijät tähän vaikuttaa.