Two-Step Spin-Transition Iron(III) Compound with a Wide [High Spin-Low Spin] Plateau

A new iron(III) coordination compound exhibiting a two-step spin-transition behavior with a remarkably wide [HS-LS] plateau of about 45 K has been synthesized from a hydrazino Schiff-base ligand with an N,N,O donor set, namely 2-methoxy-6-(pyridine-2-ylhydrazonomethyl) phenol (Hmph). The single-crystal X-ray structure of the coordination compound {[Fe(mph)(2)](ClO4)(MeOH)(0.5)(H2O)(0.5)}(2) (1) determined at 150 K reveals the presence of two slightly different iron(III) centers in pseudo-octahedral environments generated by two deprotonated tridentate mph ligands. The presence of hydrogen bonding interactions, instigated by the well-designed ligand, may justify the occurrence of the abrupt transitions. 1 has been characterized by temperature-dependent magnetic susceptibility measurements, EPR spectroscopy, differential scanning calorimetry, and Fe-51 Mossbauer spectroscopy, which all confirm the occurrence of a two-step transition. In addition, the iron(III) species in the high-spin state has been trapped and characterized by rapid cooling EPR studies.

Projected shell model description for high-spin states in neutron-rich Fe isotopes

A systematic study of neutron-rich even-even Fe isotopes with a neutron number from 32 to 42 is carried out by using the projected shell model. Calculations are performed up to the spin I=20 state. Irregularities found in the yrast spectra and in B (E2) values are discussed in terms of neutron excitations to the high-j orbital g(9/2). Furthermore, the neutron two-quasiparticle structure of a low-K negative-parity band and the proton two-quasiparticle structure of a high-K positive-parity band are predicted to exist near the yrast region. Our study reveals a soft nature for the ground state of N approximate to 40 isotopes and emphasizes the important role of the neutron g(9/2) orbital in determining the structure properties for both low- and high-spin states in these nuclei.

High-spin states in Pt-190

The level structure of Pt-190 has been studied experimentally using the Yb-176 (O-18, 4n) reaction at beam energies of 88 and 95 MeV. gamma-gamma-t coincidence measurements were carried out. Based on the analysis of gamma-gamma coincidence relationships, the level scheme of Pt-190 is extended to high-spin states. A new structure built on the 3413.6 keV 14(+) state has been observed, and the vi(13/2)(-2) vh(9/2)(-1) vj (j = p(3/2) or f(5/2)) configuration is tentatively assigned to it.

High-spin states in Au-188: Further evidence for nonaxial shape

The high-spin level structure of Au-188 has been investigated via the Yb-173(F-19,4n gamma) reaction at beam energies of 86 and 90 MeV. The previously reported level scheme has been modified and extended significantly. A new I-pi = 20(+) state associated with pi h(11/2)(-1) circle times nu i(13/2)(-2)h(9/2)(-1) configuration and two new rotational bands, one of which is built on the pi h(9/2) circle times nu i(13/2) configuration, have been identified. The prolate-to-oblate shape transition through triaxial shape has been proposed to occur around Au-188 for the pi h(9/2) circle times nu i(13/2) bands in odd-odd Au isotopes. Evidence for pi h(11/2)(-1) circle times nu i(13/2)(-1) structure of nonaxial shape with gamma < -70 degrees has been obtained by comparison with total Routhian surface and cranked-shell-model calculations.

A rule to design high spin molecules with hetero-spin centers

The series of biradicals with m-phenylene coupling unit and hetero-spin centers were calculated compared with those possessing home-spin centers using AM1-CI method. A simple rule was proposed to design high spin molecules with ferromagnetic coupling unit and hetero-spin centers. Two neutral (or charged) hetero-spin centers resulted in high spin ground state, one neutral and another charged hetero-spin centers correspond to low spin ground state. The latter was ascribed to the huge splitting of two partially occupied molecular orbitals.

The intermolecular coupling through space for stacked high spin molecules

Intermolecular ferromagnetic interactions in two stacking models for the dimer of high spin molecules are investigated by means of AM1-CI approach. It is shown that the stability of high spin ground state versus low spin state can be simply traced back to the number and the extent of atoms with reversed signs of pi-spin density in neighboring molecules coupled to each other in shortest distance.

SPIN AND VALENCE STATE EQUILIBRIA OF COBALT AND MAGNETIC-PROPERTIES OF LACOO3

On the basis of the spin and valence state equilibria and superexchange interaction of the various cobalt ions in LaCoO3, an approximate semiempirical formula has been proposed and used to calculate magnetic susceptibilities of LaCoO3 over a wide temperature range (100-1200 K). The results indicate that there are thermodynamic equilibria between the low spin state Co(III) (t2g6e(g)0) ion, the high spin state Co3+ (t2g4e(g)2) ion, the Co(II) (t2g6e(g)1) ion and the Co(IV) (t2g5e(g)0) ion in LaCoO3. The energy difference between the low spin state Co(III) and the high spin state Co3+ is about 0.006 eV. The content of the low spin state Co(III) ion is predominant in LaCoO3 and the content of the high spin state Co3+ ion varies with temperature, reaching a maximum at about 350 K, then decreasing gradually with increasing temperature. At low temperature the contents of the Co(II) ion and the Co(IV) ion in LaCoO3 are negligible, while above 200 K the contents of both the Co(II) ion and the Co(IV) ion increase with increasing temperature; however, the content of the Co(II) ion always is larger than that of the Co(IV) ion at any temperature. These calculated results are in good agreement with experimental results of the Mossbauer effect, magnetic susceptibility and electrical conductivity of LaCoO3.