Search results for "crossover"
showing 10 items of 658 documents
Anomalous diffusion in polymer melts
2002
Abstract We present a study of the anomalous diffusion regimes in polymer melt dynamics performing a Monte Carlo (MC) simulation of the bond-fluctuation lattice model. Special emphasis is laid on the crossover from a Rouse-like motion to the behavior predicted by reptation theory. For the longest chains of N=400 the high statistical accuracy of the data allows for clear identification of the subdiffusive regimes in the center of mass motion and the monomer displacement. They are well compatible with those predicted by reptation theory. Furthermore a detailed analysis of the different short time anomalous diffusion regimes in the melt dynamics of polymer chains is presented and it is shown t…
Self-diffusion in polymer solutions using the bond-fluctuation MC-algorithm
1991
Abstract A lattice Monte Carlo study of the self-diffusion of polymer chains in an athermal solution of equal chains is presented. The examined chain lengths, N (= 20–200), and volume fractions, φ (= 0.025-0.5), cover the range from dilute solution to concentrated solution, respectively. The dynamics show a gradual crossover from Rouse to reptation-like behaviour. Analysing the data according to a scaling theory and taking into account the density dependence of the microscopic length and time-scales, an almost perfect scaling of the self-diffusion coefficient is achieved. The high statistical accuracy of the data (103–104 chains per parameter combination) was obtainable by using a transpute…
Direct monitoring of spin state in dinuclear iron(II) coordination compounds
2001
So far there has been no direct method to determine the spin state of molecules in dinuclear iron(II) compounds. The molecular fractions of high-spin (HS) and low-spin (LS) species have been deduced from magnetic susceptibility and zero-field Mossbauer spectroscopy data irrespective of whether they belong to LS–LS, LS–HS and HS–HS pairs. However, the distinction of pairs becomes possible if Mossbauer measurements are carried out in an external magnetic field. The proposed method opens new possibilities in the study of spin crossover phenomena in dinuclear compounds.
Thermal, Pressure and Light Induced Spin Transition in the Two-Dimensional Coordination Polymer [Fe(pmd)2[Cu(CN)2]2]
2008
[EN] A complete structural, calorimetric, and magnetic characterisation of the 2D coordination spin crossover polymer {Fe(pmd)(2)[Cu(CN)(2)](2)} is reported. The crystal structure has been investigated below room temperature at 180 K and 90 K, and at 30 K after irradiating the sample at low temperature with green light ( lambda = 532 nm). The volume cell contraction through the thermal spin transition is only 18 angstrom(3) which is lower than the usually observed value of around 25-30 angstrom(3) while the average Fe-N bond distances decrease by the typical value of about 0.19 angstrom. The structural data of the irradiated state indicate that the high spin state is well induced since the …
Pressure-induced cooperative spin transition in ironII 2D coordination polymers: room-temperature visible spectroscopic study.
2011
For the 2D coordination polymers [Fe(3-Fpy)(2)M(II)(CN)(4)] (M(II) = Ni, Pd, Pt), the pressure-induced spin crossover behavior has been investigated at 298 K by monitoring the distinct optical properties associated with each spin state. Cooperative first-order spin transition characterized by a piezohysteresis loop ca. 0.1 GPa wide was observed for the three derivatives. Application of the mean field regular solution theory has enabled estimation of the cooperative parameter, Γ(p), and the enthalpy, ΔH(HL)(p), associated with the spin transition for each derivative. These values, found in the intervals 6.8-7.9 and 18.6-20.8 kJ mol(-1), respectively, are consistent with those previously repo…
Spin-State-Dependent Redox-Catalytic Activity of a Switchable Iron(II) Complex
2017
The spin state of catalytically active 3d metal centers plays a significant role for their activity in enzymatic processes and organometallic catalysis. Here we report on the catalytic activity of a Fe(II) coordination compound that can undergo a cooperative switch between low-spin (LS) and high-spin (HS) states. Catalytic measurements within 291 - 318 K temperature region reveal a drastic drop of the catalytic activity upon conversion of metallic centers from the LS to the HS form. For a thermoswitchable [Fe(NH2trz)3]Br2 complex (Tup = 305 K), an activation energy is found to be considerably lower for the LS state (158 kJ mol-1) comparing to the HS state (305 kJ mol-1). Mossbauer analysis …
Anisotropic Effect after Stretching of the Spin-Crossover Compound [Fe(II)(2,6-bis-(benzimidazol-2′-yl)pyridine)2] (C1O4)2 in Polyvinylalcohol Polyme…
1999
Abstract [Fe(II)(2,6-bis-(benzimidazol-2′-yl)-pyridine)2](C1O4)2 diffused into a poly(vinyl)alcohol polymer matrix, exhibits an thermally induced spin-crossover. After stretching the matrix, the compound orients itself in the matrix. Polarised UV/VIS spectra measured parallel and perpendicular to the stretching direction allowed to calculate the distortion of the molecule in the matrix by means of semi-empirical PPP SCF-CI calculations.
Bistable Hofmann-Type FeII Spin-Crossover Two-Dimensional Polymers of 4-Alkyldisulfanylpyridine for Prospective Grafting of Monolayers on Metallic Su…
2021
Aiming at investigating the suitability of Hofmann-type two-dimensional (2D) coordination polymers {FeII(Lax)2[MII(CN)4]} to be processed as single monolayers and probed as spin crossover (SCO) junctions in spintronic devices, the synthesis and characterization of the MII derivatives (MII = Pd and Pt) with sulfur-rich axial ligands (Lax = 4-methyl- and 4-ethyl-disulfanylpyridine) have been conducted. The thermal dependence of the magnetic and calorimetric properties confirmed the occurrence of strong cooperative SCO behavior in the temperature interval of 100-225 K, featuring hysteresis loops 44 and 32.5 K/21 K wide for PtII-methyl and PtII/PdII-ethyl derivatives, while the PdII-methyl deri…
Pressure effect studies in molecular magnetism
2004
We report on temperature dependent magnetic susceptibility and Mossbauer effect studies of the influence of hydrostatic pressure (up to 1.2 GPa) on dynamic electronic structure phenomena in 3d transition metal coordination compounds. The systems under investigation are mononuclear spin crossover compounds of iron (II) and chromium (II), dinuclear complexes of iron (II) exhibiting coexistence of intramolecular antiferromagnetic coupling and thermal spin crossover, 1D, 2D and 3D polynuclear spin crossover complexes of iron (II), a valence tautomeric system of cobalt (II) showing a thermal transition from a high spin [CoII (semiquinone)] to a low spin [CoII (catecholate)] species on lowering t…
Molecular magnetism, quo vadis? A historical perspective from a coordination chemist viewpoint☆
2017
Abstract Molecular magnetism has travelled a long way from the pioneering studies on electron exchange and double exchange or spin crossover and valence tautomerism in small oligonuclear complexes, from mono- to di- and tetranuclear species, to the current investigations about magnetic anisotropy and spin dynamics or quantum coherence of simple mono- or large polynuclear complexes, behaving as switchable bistable molecular nanomagnets for potential applications in information data storage and processing. In this review, we focus on the origin and development of the research in the field of molecular magnetism from a coordination chemistry viewpoint, which dates back to the establishment of …