Electronic structure and magnetic interactions of the spin-chain compounds Ca2CuO3 and Sr2CuO3

The results are presented of a combined periodic and cluster model approach to the electronic structure and magnetic interactions in the spin-chain compounds Ca2CuO3 and Sr2CuO3. An extended t-J model is presented that includes in-chain and interchain hopping and magnetic interaction processes with parameters extracted from ab initio calculations. For both compounds, the in-chain magnetic interaction is found to be around -240 meV, larger than in any of the other cuprates reported in the literature. The interchain magnetic coupling is found to be weakly antiferromagnetic, -1 meV. The effective in-chain hopping parameters are estimated to be ~650 meV for both compounds, whereas the value of the interchain hopping parameter is 30 meV for Sr2CuO3 and 40 meV for Ca2CuO3, in line with the larger interchain distance in the former compound. These effective parameters are shown to be consistent with expressions recently suggested for the Néel temperature and the magnetic moments, and with relations that emerge from the t-J model Hamiltonian. Next, we investigate the physical nature of the band gap. Periodic calculations indicate that an interpretation in terms of a charge-transfer insulator is the most appropriate one, in contrast to the suggestion of a covalent correlated insulator recently reported in the literature.

Ground- and excited-state properties of M-center oxygen vacancy aggregates in the bulk and the surface of MgO

Aggregates of oxygen vacancies (F centers) represent a particular form of point defects in ionic crystals. In this study we have considered the combination of two oxygen vacancies, the M center, in the bulk and on the surface of MgO by means of cluster model calculations. Both neutral and charged forms of the defect M and M+ have been taken into account. The ground state of the M center is characterized by the presence of two doubly occupied impurity levels in the gap of the material; in M+ centers the highest level is singly occupied. For the ground-state properties we used a gradient corrected density functional theory approach. The dipole-allowed singlet-to-singlet and doublet-to-doublet electronic transitions have been determined by means of explicitly correlated multireference second-order perturbation theory calculations. These have been compared with optical transitions determined with the time-dependent density functional theory formalism. The results show that bulk M and M+ centers give rise to intense absorptions at about 4.4 and 4.0 eV, respectively. Another less intense transition at 1.3 eV has also been found for the M+ center. On the surface the transitions occur at 1.6 eV (M+) and 2 eV (M). The results are compared with recently reported electron energy loss spectroscopy spectra on MgO thin films.

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

Microscopic derivation of a NN*(1440) potential

We derive a NN*(1440) potential from a nonrelativistic quark-quark interaction and a quark cluster model for the baryons. By making use of the Born-Oppenheimer approximation, we examine quark Pauli correlations in detail. A comparison with the NN potential derived in the same framework is done. This makes it possible to emphasize the role of quark antisymmetry beyond baryon antisymmetry and to discuss the use of phenomenological NN*(1440) baryonic potentials.

Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Logistiikkayrityksen kuljetussuunnittelun kehittäminen

Työn tavoitteena oli selvittää Transpoint Cargon kuljetussuunnittelun nykytila ja kuljetussuunnittelijoiden välisten vastuiden jakaantuminen. Työn tavoitteena oli lisäksi rakentaa kuljetussuunnittelulle alueellinen toimintamalli yrityksen asettamien rajoitteiden mukaisesti. Kuljetussuunnittelun tilaa tutkittiin haastatteluiden, visuaalisen analysoinnin, oman työkokemuksen ja tuotevirta-analyysin avulla. Kuljetussuunnittelun suurimmat kehitystarpeet löytyivät vastuiden loogisemmasta jakamisesta ja suunnittelijoiden tavasta ohjata autoja. Kehitysehdotuksena nykytilanteen parantamiseksi työssä esitetään kuljetussuunnittelijoiden työtehtävien jakaminen klusteri mallin mukaisesti. Klusteri malliin perustuen työssä esitetään kolme eri vaihtoehtoa kuljetussuunnittelun alueellisen toimintamallin toteuttamiseksi.

Syntyykö Suomeen puulaaksoja - Suomen puutuoteteollisuuden pk-yritysten tila ja tulevaisuus

Metsäteollisuus on tullut Suomeen ulkomaisen pääoman ja tietotaidon avulla vajaat kaksisataa vuotta sitten. Se on toiminut melkein koko jatkosodan jälkeisen ajan suojatussa ympäristössä ja ulkomaisesta kilpailusta riippumattomassa toimintaympäristössä. Kuten Porter ja muut ovat todistaneet, tällainen toimintaympäristö ei kehitä kansainvälisesti kilpailukykyistä teollisuutta globaaleilla markkinoilla. Liittyminen Euroopan unioniin ja sittemmin Euroopan rahaliittoon saattoi puunjalostusteollisuuden täysin uudenlaiseen kilpailutilanteeseen. Sama tapahtui myös alan pk-yrityksille, jotka olivat joutuneet toimimaan heikosti kilpailluilla raaka-ainemarkkinoilla. Tutkimus on tulevaisuudentutkimus, jossa tutkimusongelmia lähestytään kolmen teorian avulla. Porterin klusteriteoria tarjoaa mahdollisuuden arvioida metsäteollisuutta sekä kokonaisuutena että toimivana monimuotoisena organisaationa, jossa kustannukset ja hinta muodostuvat arvoketjun toimijoiden osakustannuksista. Bionomiateoria eli darvinistinen talousteoria testaa suomalaisen puunjalostusteollisuuden pk-yritysten kilpailukykyä ja paineita hakeutua edullisemmille toiminta- alueille. Evoluutioteoria tarkastelee sukupolvenvaihdoksen problematiikkaa. Sukupolvenvaihdoksen onnistuminen muodostuu puutoimialan elämän ja kuoleman kysymykseksi. Tämä on etenkin pk-yrityksiä kohtaava ongelma. Asiaa selvitettiin Mauno Rintalan suorittamalla kyselytutkimuksella Puuteollisuusyrittäjien jäsenistön keskuudessa. Ongelma johtuu suurista sodan jälkeen syntyneistä ikäluokista. Nämä vuosina 1945– 50 syntyneet ovat siirtymässä eläkkeelle vuosien 2005 ja 2015 välillä. Kyseisissä ikäluokissa yritystiheys on noin kaksi kertaa suurempi kuin sen jälkeisissä ikäluokissa. Suoritetun kyselyn sekä muiden suomalaisten ja kansainvälisten tutkimusten perusteella näyttää siltä, että eläkkeelle siirryttäessä vain noin 30 %:lla yrityksistä on jatkaja tiedossa suvusta tai lähipiiristä. Tämä merkitsee sitä, että 70 % eläköityvän ikäluokan omistamista yrityksistä poistuu pysyvästi markkinoilta. Suomessa poistuma merkitsee noin 40 % koko yritysvarannosta eli noin 80 000 yritystä. Tilastot toimivien yritysten määrästä ovat kuitenkin hyvin ristiriitaisia, joten todellista määrää on mahdoton arvioida. Noin suuren määrän poistuminen markkinoilta uhkaa jo hyvinvointivaltion perusrakenteita. Tutkimustulos edellyttää nopeita toimenpiteitä teollisten pkyritysten pelastamiseksi ja säilyttämiseksi Suomessa. Sukupolvenvaihdoksen onnistuminen on tässä prosessissa ensiarvoisessa asemassa. Kaikkien edellä mainittujen yritysten poistuminen markkinoilta edellyttäisi noin 400 000 uuden yrityksen perustamista, koska ainoastaan noin 20 % yrityksistä selviää ensimmäiset kolme vuotta. Tutkimukseen perustuen esitetään prosessimalli sukupolvenvaihdoksen suorittamiseksi. Suomen tärkeimmissä kilpailijamaissa valtioiden metsäomistus on määräävässä asemassa. Meillä metsät ovat yksityisessä omistuksessa ja vain pieni osa valtion omistuksessa. Puumarkkinat toimivat markkinatalouden ehdoilla ilman valtion ohjausta. Ongelmaksi on kehittymässä puun saanti. Metsänomistus on sukupolvien myötä hajaantunut hyvin pieniksi metsälöiksi. Nykyiset metsänomistajat asuvat kaupungeissa ja ovat pääosin palkkatyössä. He eivät ole samalla tavoin riippuvaisia puutuloista kuin heidän esi-isänsä. Metsäverotuksen uudistuminen lisää puun saannin epävarmuutta. Se on muuttumassa pinta-alaverotuksesta puun myynnin verotukseen. Puun myynti on vilkasta ennen järjestelmien vaihtumista ja vähäisempää sen jälkeen. Myös näitä ongelmia on pyritty ratkomaan uudenlaisen metsänomistusmallin avulla. Puuteollisuus on hyvin vanha teollisuudenala. Raaka-aine muodostaa määräävän osan kustannuksista. Muutokset ovat hitaita ja todelliset innovaatiot pitkäkestoisia. Uusia innovaatioita tapahtuu harvoin. Kannattavuutta parannetaan tuoteprosessien ja arvoketjujen kehittämisen kautta. Yhteiskunnan osuus alan kehittämisessä ja säilyttämisessä on ratkaiseva. Asioiden moninaisuus tekee tutkimuksen vaikeaksi, mutta sitäkin tärkeämmäksi kansantalouden kannalta. Tällaisissa suurissa murroksissa korostuu kaikkien päättävien tahojen henkinen valmius ja tahto tehdä oikeita ratkaisuja oikeaan aikaan.

Ab initio theoretical comparative study of magnetic coupling in KNiF3 and K2NiF4s

The origin of magnetic coupling in KNiF3 and K2 NiF4 is studied by means of an ab initio cluster model approach. By a detailed study of the mapping between eigenstates of the exact nonrelativistic and spin model Hamiltonians it is possible to obtain the magnetic coupling constant J and to compare ab initio cluster-model values with those resulting from ab initio periodic Hartree-Fock calculations. This comparison shows that J is strongly determined by two-body interactions; this is a surprising and unexpected result. The importance of the ligands surrounding the basic metal-ligand-metal interacting unit is reexamined by using two different partitions and the constrained space orbital variation method of analysis. This decomposition enables us to show that this effect is basically environmental. Finally, dynamical electronic correlation effects have found to be critical in determining the final value of the magnetic coupling constant.

Local character of magnetic coupling in ionic solids

Magnetic interactions in ionic solids are studied using parameter-free methods designed to provide accurate energy differences associated with quantum states defining the Heisenberg constant J. For a series of ionic solids including KNiF3, K2NiF4, KCuF3, K2CuF4, and high- Tc parent compound La2CuO4, the J experimental value is quantitatively reproduced. This result has fundamental implications because J values have been calculated from a finite cluster model whereas experiments refer to infinite solids. The present study permits us to firmly establish that in these wide-gap insulators, J is determined from strongly local electronic interactions involving two magnetic centers only thus providing an ab initio support to commonly used model Hamiltonians.

Ab Initio study of magnetic interactions in the KCuF3 and K2CuF4 low-dimensional Systems

The ab initio cluster model approach has been used to study the electronic structure and magnetic coupling of KCuF3 and K2CuF4 in their various ordered polytype crystal forms. Due to a cooperative Jahn-Teller distortion these systems exhibit strong anisotropies. In particular, the magnetic properties strongly differ from those of isomorphic compounds. Hence, KCuF3 is a quasi-one-dimensional (1D) nearest neighbor Heisenberg antiferromagnet whereas K2CuF4 is the only ferromagnet among the K2MF4 series of compounds (M=Mn, Fe, Co, Ni, and Cu) behaving all as quasi-2D nearest neighbor Heisenberg systems. Different ab initio techniques are used to explore the magnetic coupling in these systems. All methods, including unrestricted Hartree-Fock, are able to explain the magnetic ordering. However, quantitative agreement with experiment is reached only when using a state-of-the-art configuration interaction approach. Finally, an analysis of the dependence of the magnetic coupling constant with respect to distortion parameters is presented.

Electronic structure and magnetic interactions of the spin-chain compounds Ca2CuO3 and Sr2CuO3

The results are presented of a combined periodic and cluster model approach to the electronic structure and magnetic interactions in the spin-chain compounds Ca2CuO3 and Sr2CuO3. An extended t-J model is presented that includes in-chain and interchain hopping and magnetic interaction processes with parameters extracted from ab initio calculations. For both compounds, the in-chain magnetic interaction is found to be around -240 meV, larger than in any of the other cuprates reported in the literature. The interchain magnetic coupling is found to be weakly antiferromagnetic, -1 meV. The effective in-chain hopping parameters are estimated to be ~650 meV for both compounds, whereas the value of the interchain hopping parameter is 30 meV for Sr2CuO3 and 40 meV for Ca2CuO3, in line with the larger interchain distance in the former compound. These effective parameters are shown to be consistent with expressions recently suggested for the Néel temperature and the magnetic moments, and with relations that emerge from the t-J model Hamiltonian. Next, we investigate the physical nature of the band gap. Periodic calculations indicate that an interpretation in terms of a charge-transfer insulator is the most appropriate one, in contrast to the suggestion of a covalent correlated insulator recently reported in the literature.

Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Ground- and excited-state properties of M-center oxygen vacancy aggregates in the bulk and the surface of MgO

Aggregates of oxygen vacancies (F centers) represent a particular form of point defects in ionic crystals. In this study we have considered the combination of two oxygen vacancies, the M center, in the bulk and on the surface of MgO by means of cluster model calculations. Both neutral and charged forms of the defect M and M+ have been taken into account. The ground state of the M center is characterized by the presence of two doubly occupied impurity levels in the gap of the material; in M+ centers the highest level is singly occupied. For the ground-state properties we used a gradient corrected density functional theory approach. The dipole-allowed singlet-to-singlet and doublet-to-doublet electronic transitions have been determined by means of explicitly correlated multireference second-order perturbation theory calculations. These have been compared with optical transitions determined with the time-dependent density functional theory formalism. The results show that bulk M and M+ centers give rise to intense absorptions at about 4.4 and 4.0 eV, respectively. Another less intense transition at 1.3 eV has also been found for the M+ center. On the surface the transitions occur at 1.6 eV (M+) and 2 eV (M). The results are compared with recently reported electron energy loss spectroscopy spectra on MgO thin films.

Ionic-covalent transition in titanium oxides

The nature of the chemical bond in three titanium oxides of different crystal structure and different formal oxidation state has been studied by means of the ab initio cluster-model approach. The covalent and ionic contributions to the bond have been measured from different theoretical techniques. All the analysis is consistent with an increasing of covalence in the TiO, Ti2O3, and TiO2 series as expected from chemical intuition. Moreover, the use of the ab initio cluster-model approach combined with different theoretical techniques has permitted us to quantify the degree of ionic character, showing that while TiO can approximately be described as an ionic compound, TiO2 is better viewed as a rather covalent oxide.

Some Aspects of Domain Specific Conceptual Modeling for Simulation of Logistic Terminal Operations

When simulation modeling is used for performance improvement studies of complex systems such as transport terminals, domain specific conceptual modeling constructs could be used by modelers to create structured models. A two stage procedure which includes identification of the problem characteristics/cluster - ‘knowledge acquisition’ and identification of standard models for the problem cluster – ‘model abstraction’ was found to be effective in creating structured models when applied to certain logistic terminal systems. In this paper we discuss some methods and examples related the knowledge acquisition and model abstraction stages for the development of three different types of model categories of terminal systems