An infrared spectroscopic study of the low-spin-high-spin transition in FexMn1-x(Phen)2(NCS)2: A composition-induced change in the order of the spin-state transition

Infrared spectroscopy provides a valuable tool to investigate the spin-state transition in Fe(II) complexes of the type Fe(Phen)2(NCS)2. With progressive substitution of Fe by Mn, the first-order transition changes over to a second-order transition, with a high residual population of the high-spin state even at very low temperatures

Models of the proton spin structure

A phenomenological model of spin sharing by the constituents of a proton is constructed, based on the recent EMC measurement of the spin dependent structure function and knowledge of the unpolarized parton densities.

Hysteresis in model spin system

The aim of this paper is to construct a nonequilibrium statistical‐mechanics theory to study hysteresis in ferromagnetic systems. We study the hysteretic response of model spin systems to periodic magnetic fields H(t) as a function of the amplitude H0 and frequency Ω. At fixed H0, we find conventional, squarelike hysteresis loops at low Ω, and rounded, roughly elliptical loops at high Ω, in agreement with experiments. For the O(N→∞), d=3, (Φ2)2 model with Langevin dynamics, we find a novel scaling behavior for the area A of the hysteresis loop, of the form A∝H0.660Ω0.33. We carry out a Monte Carlo simulation of the hysteretic response of the two‐dimensional, nearest‐neighbor, ferromagnetic Ising model. These results agree qualitatively with the results obtained for the O(N) model.

Homonuclear NOE in spatially periodic spin systems

The nuclear Overhauser effect equations are solved analytically for a homonuclear group of spins whose sites are periodically arranged, including the special cases where the spins lie at the vertices of a regular polygon and on a one-dimensional lattice. t is shown that, for long correlation times, the equations governing magnetization transfer resemble a diffusion equation. Furthermore the deviation from exact diffusion is quantitatively related to the molecular tumbling correlation time. Equations are derived for the range of magnetization travel subsequent to the perturbation of a single spin in a lattice for both the case of strictly dipolar relaxation and the more general situation where additional T1 mechanisms may be active. The theory given places no restrictions on the delay (or mixing) times, and it includes all the spins in the system. Simulations are presented to confirm the theory.

Lumettoman maan routaolojen mallintaminen ja ennustettavuus muuttuvassa ilmastossa

Raportissa on arvioitu ilmastonmuutoksen vaikutusta Suomen maaperän talviaikaiseen jäätymiseen lämpösummien perusteella. Laskelmat kuvaavat roudan paksuutta nimenomaisesti lumettomilla alueilla, esimerkiksi teillä, joilta satanut lumi aurataan pois. Luonnossa lämpöä eristävän lumipeitteen alla routaa on ohuemmin kuin tällaisilla lumettomilla alueilla. Toisaalta luonnollisessa ympäristössä paikalliset erot korostuvat johtuen mm. maalajeista ja kasvillisuudesta. Roudan paksuudet laskettiin ensin perusjakson 1971–2000 ilmasto-oloissa talviaikaisten säähavaintotietoihin pohjautuvien lämpötilojen perusteella. Sen jälkeen laskelmat toistettiin kolmelle tulevalle ajanjaksolle (2010–2039, 2040–2069 ja 2070–2099) kohottamalla lämpötiloja ilmastonmuutosmallien ennustamalla tavalla. Laskelman pohjana käytettiin 19 ilmastomallin A1B-skenaarioajojen keskimäärin simuloimaa lämpötilan muutosta. Tulosten herkkyyden arvioimiseksi joitakin laskelmia tehtiin myös tätä selvästi heikompaa ja voimakkaampaa lämpenemisarviota käyttäen. A1B-skenaarion mukaisen lämpötilan nousun toteutuessa nykyisiä mallituloksia vastaavasti routakerros ohenee sadan vuoden aikana Pohjois-Suomessa 30–40 %, suuressa osassa maan keski- ja eteläosissa 50–70 %. Jo lähivuosikymmeninä roudan ennustetaan ohentuvan 10–30 %, saaristossa enemmän. Mikäli lämpeneminen toteutuisi voimakkaimman tarkastellun vaihtoehdon mukaisesti, roudan syvyys pienenisi tätäkin enemmän. Roudan paksuuden vuosienvälistä vaihtelua ja sen muuttumista tulevaisuudessa pyrittiin myös arvioimaan. Leutoina talvina routa ohenee enemmän kuin normaaleina tai ankarina pakkastalvina. Päivittäistä sään vaihtelua simuloineen säägeneraattorin tuottamassa aineistoissa esiintyi kuitenkin liian vähän hyvin alhaisia ja hyvin korkeita lämpötiloja. Siksi näitten lämpötilatietojen pohjalta laskettu roudan paksuuskin ilmeisesti vaihtelee liian vähän vuodesta toiseen. Kelirikkotilanteita voi esiintyä myös kesken routakauden, jos useamman päivän suojasää ja samanaikainen runsas vesisade pääsevät sulattamaan maata. Tällaiset routakauden aikana sattuvat säätilat näyttävätkin yleistyvän lähivuosikymmeninä. Vuosisadan loppua kohti ne sen sijaan maan eteläosissa jälleen vähenevät, koska routakausi lyhenee oleellisesti. Tulevia vuosikymmeniä koskevien ilmastonmuutosennusteiden ohella routaa ja kelirikon esiintymistä on periaatteessa mahdollista ennustaa myös lähiaikojen sääennusteita hyödyntäen. Pitkät, viikkojen tai kuukausien mittaiset sääennusteet eivät tosin ole ainakaan vielä erityisen luotettavia, mutta myös lyhyemmistä ennusteista voisi olla hyötyä mm. tienpitoa suunniteltaessa.

Ab initio molecular orbital calculations on ion-molecule and ion pair-molecule complexes of the water-lithium cyanide system

Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets were performed on a series of ion-molecule and ion pair-molecule complexes for the H2O + LiCN system. Stabilisation energies (with counter-poise corrections), geometrical parameters, internal force constants and harmonic vibrational frequencies were evaluated for 16 structures of interest. Although the interaction energies are smaller, the geometries and relative stabilities of the monohydrated contact ion pair are reminiscent of those computed for the complexes of the individual ions. Thus, interaction of the oxygen lone pair with lithium leads to a highly stabilised C2v structure, while the coordination of water to the cyanide ion involves a slightly non-linear hydrogen bond. Symmetrical bifurcated structures are computed to be saddle points on the potential energy surface, and to have an imaginary frequency for the rocking mode of the water molecule. On optimisation the geometries of the solvent shared ion pair structures (e.g. Li+cdots, three dots, centered OH2cdots, three dots, centered CN−) revealed a proton transfer from the water molecule leading to hydrogen bonded forms such as Li-O-Hcdots, three dots, centered HCN. The variation in the force constants and harmonic frequencies in the various structures considered are discussed in terms of ion-molecular and ion pair-molecule interactions.

Activation barriers for d.c. conductivity in ionic glasses: Classical calculations using the small-cluster approximation

A small-cluster approximation has been used to calculate the activation barriers for the d.c. conductivity in ionic glasses. The main emphasis of this approach is on the importance of the hitherto ignored polarization energy contribution to the total activation energy. For the first time it has been demonstrated that the d.c. conductivity activation energy can be calculated by considering ionic migration to a neighbouring vacancy in a smali cluster of ions consisting of face-sharing anion polyhedra. The activation energies from the model calculations have been compared with the experimental values in the case of highly modified lithium thioborate glasses.

Chiral polyhydroxylated tetrahydrothiophene derivatives: novel synthesis and structural elucidation by X-ray crystallography, NMR spectroscopy and molecular mechanics calculations

The dideoxygenation reaction of 1,3;4,6-di-O-alkylidene-2,5-di-S-methylthiocarbonyl-D-mannitol derivatives under Barton-McCombie reaction conditions gave the hexahydrodipyranothiophenes 4 and 7 instead of the expected 2,5-dideoxy products. Structural and conformational information on these novel derivatives has been obtained by NMR spectroscopy, single-crystal X-ray crystallography and molecular mechanics calculations.

Direct versus kinetic exchange in multiband models for organic ferromagnetism

Multiband Hubbard and Pariser-Parr-Pople calculations have been carried out on mixed donor-acceptor (DA) stacks with doubly degenerate acceptor orbitals and nondegenerate donor orbitals at two-thirds filling. Model exact results for 2, 3, and 4 DA units show that McConnell's prediction of high-spin ground states in these systems is, in general, incorrect. The larger phase space available for the low-spin states leads to their kinetic stabilization in preference to high-spin states. However, for large electron-correlation strengths, the direct exchange dominates over the kinetic exchange resulting in a high-spin ground state

Excitation and relaxation energies of trans-stilbene: Confined singlet, triplet, and charged bipolarons

The π-electronic excitations and excited-state geometries of trans-stilbene (tS) are found by combining exact solutions of the Pariser-Parr-Pople (PPP) model and semiempirical Parametric Method 3 (PM3) calculations. Comprehensive comparisons with tS spectra are obtained and related to the fluorescence and topological alternation of poly(paraphenylenevinylene) (PPV). The one-photon absorption and triplet of tS correspond, respectively, to singlet and triplet bipolarons confined to two phenyls, while the tS2- ground state is a confined charged bipolaron. Independent estimates of the relaxation energy between vertical and adiabatic excitation show the bipolaron binding energy to depend on both charge and spin, as expected for interacting π electrons in correlated or molecular states. Complete configuration interaction within the PPP model of tS accounts for the singlet-triplet gap, for the fine-structure constants and triplet-triplet spectra, for two-photon transitions and intensities, and for one-photon spectra and the radiative lifetime, although the relative position of nearly degenerate covalent and ionic singlets is not resolved. The planar PM3 geometry and low rotational barrier of tS agree with resolved rotational and vibrational spectra in molecular beams. PM3 excitation and relaxation energies for tS bipolarons are consistent with experiment and with PPP results. Instead of the exciton model, we interpret tS excitations in terms of states that are localized on each ring or extended over an alternating chain, as found exactly in Hückel theory, and find nearly degenerate transitions between extended and localized states in the singlet, triplet, and dianion manifolds. The large topological alternation of the extended system increases the ionicity and interchanges the order of the lowest one- and two-photon absorption of PPV relative to polyenes.

Top-spin analysis of new scalar and tensor interactions in e(+)e(-) collisions with beam polarization

We utilize top polarization in the process e(+)e(-) -> t (t) over bar at the International Linear Collider ( ILC) with transverse beam polarization to probe interactions of the scalar and tensor type beyond the standard model and to disentangle their individual contributions. Ninety percent confidence level limits on the interactions with realistic integrated luminosity are presented and are found to improve by an order of magnitude compared to the case when the spin of the top quark is not measured. Sensitivities of the order of a few times 10(-3) TeV-2 for real and imaginary parts of both scalar and tensor couplings at root s = 500 and 800 GeV with an integrated luminosity of 500 fb(-1) and completely polarized beams are shown to be possible. A powerful model-independent framework for inclusive measurements is employed to describe the spin-momentum correlations, and their C, P, and T properties are presented in a technical appendix.

Size dependence of the bulk modulus of semiconductor nanocrystals from first-principles calculations

The variation in the bulk modulus of semiconductor nanoparticles has been studied within first-principles electronic-structure calculations using the local density approximation (LDA) for the exchange correlation. Quantum Monte Carlo calculations carried out for a silicon nanocrystal Si87H76 provided reasonable agreement with the LDA results. An enhancement was observed in the bulk modulus as the size of the nanoparticle was decreased, with modest enhancements being predicted for the largest nanoparticles studied here, a size just accessible in experiments. To access larger sizes, we fit our calculated bulk moduli to the same empirical law for all materials, the asymptote of which is the bulk value of the modulus. This was found to be within 2-10% of the independently calculated value. The origin of the enhancement has been discussed in terms of Cohen's empirical law M.L. Cohen, Phys. Rev. B 32, 7988 (1985)] as well as other possible scenarios.

Quantum Properties in Transport Through Nanoscopic Rings:Charge-Spin Separation and Interference Effects

Many of the most intriguing quantum effects are observed or could be measured in transport experiments through nanoscopic systems such as quantum dots, wires and rings formed by large molecules or arrays of quantum dots. In particular, the separation of charge and spin degrees of freedom and interference effects have important consequences in the conductivity through these systems. Charge-spin separation was predicted theoretically in one-dimensional strongly inter-acting systems (Luttinger liquids) and, although observed indirectly in several materials formed by chains of correlated electrons, it still lacks direct observation. We present results on transport properties through Aharonov-Bohmrings (pierced by a magnetic flux) with one or more channels represented by paradigmatic strongly-correlated models. For a wide range of parameters we observe characteristic dips in the conductance as a function of magnetic flux which are a signature of spin and charge separation. Interference effects could also be controlled in certain molecules and interesting properties could be observed. We analyze transport properties of conjugated molecules, benzene in particular, and find that the conductance depends on the lead configuration. In molecules with translational symmetry, the conductance can be controlled by breaking or restoring this symmetry, e.g. by the application of a local external potential. These results open the possibility of observing these peculiar physical properties in anisotropic ladder systems and in real nanoscopic and molecular devices.

Ab initio molecular orbital calculations on ion pair-water complexes of metal halides and oxides

Ab initio MO calculations are performed on a series of ion-molecular and ion pair-molecular complexes of H2O + MX (MX = LiF, LiCl, NaCl, BeO and MgO) systems. BSSE-corrected stabilization energies, optimized geometrical parameters, internal force constants and harmonic vibrational frequencies have been evaluated for all the structures of interest. The trends observed in the geometrical parameters and other properties calculated for the mono-hydrated contact ion pair complexes parallel those computed for the complexes of the individual ions. The bifurcated structures are found to be saddle points with an imaginary frequency corresponding to the rocking mode of water molecules. The solvent-shared ion pair complexes have high interaction energies. Trends in the internal force constant and harmonic frequency values are discussed in terms of ion-molecular and ion-pair molecular interactions.