A mixed-valence polyoxovanadate(III,IV) cluster with a calixarene cap exhibiting ferromagnetic V(III)-V(IV) interactions

A series of compounds (cat)[V6O6(OCH3)8(calix)(CH3OH)] was obtained under anaerobic conditions and solvothermal reaction of VOSO4 with p-tert-butylcalix[4]arene (calix) in methanol using different types of bases (Et4NOH, NH4OH, pyridine, Et3N). All compounds contain the same polyoxo(alkoxo)hexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) exhibiting a mixed valence {VIIIVIV5O19} core with the so-called Lindqvist structure coordinated to a calix[4]arene macrocycle and cocrystallizing with the conjugated acid of the base (cat = Et4N+, NH4(+), pyridinium, Et3NH+) involved in the synthesis process. The structures have been fully established from X-ray diffraction on single crystals and the mixed valence state has been confirmed by bond valence sum calculations. The magnetic behavior of all compounds are the same because of the polyalkoxohexavanadate anion [V6O6(OCH3)8(calix)(CH3OH)]- (1) and have been interpreted by DFT calculations. Thus the V(III)...V(IV) interactions are found to be weakly ferromagnetic (<5.5 cm(-1)) while the V(IV)...V(IV) are antiferromagnetic (-17.6; -67.6 cm(-1)). The set of the coupling exchange parameters allows a good agreement with the magnetic experimental data.     

First dicyanamide-bridged spin-crossover coordination polymer: synthesis, structural, magnetic, and spectroscopic studies

We report here on the synthesis and characterisation of a first iron(II) spin-crossover coordination polymer with the dca spacer ligand, having the formula [Fe(aqin)2(dca)]ClO4.MeOH (aqin=8-aminoquinoline, dca=dicyanamide), which displays a two-step complete spin transition. Variable-temperature magnetic susceptibility measurements and M?ssbauer spectroscopy have revealed that the two relatively gradual steps are centred at 215 and 186 K and are separated by an inflection point at about 201 K, at which 50 % of the complex molecules undergo a spin transition. The two steps are related to the existence of two crystallographically inequivalent metal sites, as confirmed by the structural and M?ssbauer studies. The crystal structure was resolved at 293 K (HS form) and 130 K (LS form). Both spin-state structures belong to the triclinic P1 space group (Z=2). The complex assumes a linear chain structure, in which the active iron(II) sites are linked to each other by anionic dicyanamide ligands acting as chemical bridges. The Fe-Fe distances through the dca ligand are 8.119(1) and 7.835(1) A in the high-spin and low-spin structures, respectively. The polymeric chains extend along a (1, 0, -1) axis and are packed in sheets, between which the perchlorate anions and methanol molecules are inserted. The complex molecules are linked together by pi-stacking interactions and H-bonding between the H-donor aqin ligands and the perchlorate ions. These structural features provide a basis for cooperative interactions in the crystal lattice. Analysis of the two-step spin-crossover character in this compound suggests that covalent interactions through the spacer ligand do not provide the main mechanism of cooperativity.     

Investigation of the two-step spin crossover complex Fe[5-NO2-sal-(1,4,7,10)] using density functional theory

A quantum chemical study of the Fe[5-NO2-sal-(1,4,7,10)] ((1,10-bis(5-nitrosalicylaldehyde)-1,4,7,10-tetra-ezdecane-O,O',N,N',N' ',N' ')iron(II)) molecule was performed using density functional theory (DFT). Starting from the different X-ray crystallographic structures, geometry optimizations have been performed. These calculations confirmed the conformational isomerism of this complex in each spin states of the molecule ((1)A(1g) and (5)T(2g)). Each employed DFT method (B3LYP, B3LYP*, BP86, HCTH407) reproduced correctly the structural differences between the two calculated conformers when compared to the experimental structures. Furthermore, electronic polarizabilities have been calculated in each spin state and for each conformer. These calculations revealed a higher polarizability in the singlet state in agreement with the measured higher dielectric constant in this state.     

多光子过程中相位退相干时两原子布局数反转

利用全量子理论的方法,研究了存在相位退相干时多光子T-C模型中两个二能级原子与二项式光场相互作用系统中两原子的布居数反转。讨论了相位退相干系数、二项式光场系数、最大光子数、跃迁光子数对原子布居数反转的影响。结果表明：相位退相干减少了原子布居数反转的振幅、破坏了原子的量子特性。改变跃迁光子数,可以改变原子间布居数反转演化周期及演化强度。当二项式光场的最大光子数增大时,原子布居差的崩塌-回复现象就会逐渐消失。相位退相干因子不变时, 二项式光场从相干态过渡到数态过程中,原子布居的振荡频率由大变小,周期性的崩塌与回复现象逐渐消失。     

The First Principles Investigations of the Thermoelectric Properties of GaN with p- and n-Type Doping

We investigate the thermoelectric properties of GaN with p-and n-type doping by the first principles calculation and the semi-classical Boltzmann theory. We find that the power factors (S2σof p-type GaN (-3500 W/mK2) is about twice that of the n-type (-1750 W/mK2), which indicates the thermoelectric properties of p-type GaN would be better. Thermal conductivity of GaN crystal decreases rapidly as the temperature increases, but it is still too large for thermoelectric applications. The figure of merit (ZT) estimated at 1500 K is 0.134 for p-type GaN crystal and 0.062 for the n-type.     

Helical traveling waves in elastic rods

We pose the problem on free harmonic bending vibrations of an infinite rotating tubular elastic rod with an internal fluid flow, prestressed by a torque and a longitudinal force. We show that these vibrations can only be realized as traveling circular helical waves. It is shown that, for any wavelength, there exist four waves, two having the form of a left-handed helix and the other two having the form of a right-handed helix. Each of these waves propagates in the positive and negative directions of the longitudinal rod axis at different velocities. These phenomena can manifest themselves in deep-hole drill columns.     

QCD PERTURBATION THEORY AND NUCLEI (1) THE ENERGY SHIFTS OF HADRENS AND HADRONS MASS DIFFERENCE MASS DIFFERENCE

QCD perturbation theory for confined quarks and gluons (inhadrons) is discussed.Based on the equivalent potential for the quark-gluon interaction derived, the energyshifts of hadrons and hadron mass difference in MIT bag (cavity) model and correcpond-ing approximation of the w. f. with Gassian form are calculated.     

Theoretical Investigations of Nonlinear Optical Properties of Transition Metal Cluster Anions

In the framework of density functional theory （DFT）, the electronic excitations and nonlinear optical （NLO） properties of six binuclear transition metal cluster anions with the formula of [Ch2M-（μ-Ch）2-M＇CN]^2- （M = Mo, W; Ch = S, Se; M＇ = Cu, Ag） have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M＇→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M＇CN as well as those of μ-Ch→M and M＇→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M＇CN make larger contributions to the hyperpolarizability, especially to γ.