Single-crystal X-ray structure and properties of K-10[Ni-4(H2O)(2)(AsW9O34)(2)]center dot 4H(2)O

The rational synthesis and the structural and magnetic characterization of a nickel cluster are presented. The compound comprises a rhomblike Ni4O16 group encapsulated between two-heptadentate tungstoarsenate ligands [AsW9O34](9-). The crystal structure of K-10[Ni-4(H2O)(2)(AsW9O34)(2)](.)4H(2)O was solved in monoclinic, P2(1)/n symmetry, with a = 12.258(3) Angstrom, b = 21.232(4) Angstrom, c = 15.837(3) Angstrom, beta = 92.05(3)degrees, V = 4119.1(14) Angstrom(3), Z = 2, and R = 0.0862. The crystal structure of the Ni(II) derivative was compared with that of the Cu(II), Zn(II), Co(II) and Mn(II) derivatives. The Ni4O14(H2O)(2) unit in the compound shows no Jahn-Teller distortion. On the other hand, the Ni(II) derivative shows ferromagnetic exchange interactions within the Ni4O16 group (J = 7.8 cm(-1), J' = 13.7 cm(-1)) and an S = 4 ground state, the highest spin state reported in a heteropoly complex. Its redox electrochemistry has been studied in acid buffer solutions using cyclic voltammetry. It exhibited two steps of one-electron redox waves attributed to redox processes of the tungsten-oxo framework. The new catalyst showed an electrocatalytic effect on the reduction of NO2-.

Effect of configuration and conformation on the spin multiplicity in xylylene type biradicals

The singlet-triplet splitting energy gap DeltaE(S.T) = E-S - E-T is calculated for the ortho-, meta-, and para-xylylenes and their heteroatomic analogous by means of AM1-CI approach. It is shown that when the radical centers R-.(R-.=H2C.-,H2N.+- or HN.-) are twisted sufficiently Tar out of conjugation with the benzene ring, DeltaE(S.T) tends to zero or is negative, i.e, ortho-, meta-, and para-phenylenes turn into weak ferromagnetic or antiferromagnetic coupling unit, while they are strong ferromagnetic (meta-isomers) or antiferromagnetic (ortho-, para-isomers) coupling units under planar conformation. It is suggested that serious twisted conformation is not recommended candidate for the design of novel high-spin molecules with stable high-spin ground states by ortho- or para-phenylene coupling unit.

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.

Study on the energy transfer between UO22+ and Eu3+ in sol-gel derived titania matrix by luminescence spectroscopy

The TiO2 gel doped with UO22+ and Eu3+ has been prepared by a sol-gel method. The quenching of the UO22+ emission by Eu3+ and the energy transfer from the excited state of UO22+ to the ground state oh Eu3+ have been investigated. The energy transfer has been studied by the measurement of luminescence lifetime tau, calculations of energy transfer efficiency eta(ET) and energy transfer rate W-ET The experimental results indicated that the quenching is combined static and dynamic mechanism, but the static mechanism is dominant.

Luminescence and energy transfer phenomena of several rare earth ions in the CaAl2B2O7

The luminescence properties of Ce3+, Gd3+, and Tb3+ have been investigated in the compound CaAl2B2O7. The single excitation band peaking at about 320 nm and single emission band peaking at about 384 nm for Ce3+, without the characteristic doublet, are attributed to the extensive crystal-field splitting of 4f ground state. The emission of Gd3+ consists of well-known sharp lines and two weak bands around 319.5 and 325 nm. These bands are due to the coupling of Gd3+ with BO33- groups. The green emission of Tb3+ is considerably sensitized by Ce3+. Energy transfer from Ce3+ to Tb3+ in CaAl2B2O7 is efficient. (C) 1997 Elsevier Science Ltd.

NATURAL RADIATIVE LIFETIMES OF THE EXCITED-LEVELS OF THULIUM

The radiative lifetimes of eight excited levels of thulium have been measured with the method of stepwise excitation from the 4f13(F-degrees-7/2)6s2(1S0)\7/2\ ground state to the states studied using two pulsed dye lasers. Optical transients were recorded through observing fluorescences and evaluated with regard to the decay time. The accuracy of the measured lifetime values is about 10%.

CALCULATIONS OF THE EIGENVALUES OF PURE QUADRUPOLE INTERACTION IN MOSSBAUER-EFFECT STUDIES

Two approximate formulae to calculate the eigenvalues of pure quadrupole interaction in Mossbauer effect studies have been proposed and the eigenvalue coefficients in the formulae have been given for various excited states and ground states of the nucleus with different spin. All the eigenvalues of pure quadrupole interaction between both excited state and ground state of nucleus with spin I = 3/2 divided-by 9/2 and the electric-field gradient with different asymmetry parameter (eta = 0 divided-by 1.0) have been calculated by these formulae. The results show that the accuracies in all the calculations are more satisfactory or same in comparison with those obtained by the formula of Shenoy and Dunlap, especially when the asymmetry parameter of electric-field gradient is larger than 0.8 for the nucleus with spin I = 5/2.

MEASUREMENT AND CALCULATION OF SPONTANEOUS EMISSION BRANCHING RATIOS, RELATIVE OSCILLATOR-STRENGTHS, TRANSITION-PROBABILITIES AND LEVEL LIFETIMES FOR ATOMIC URANIUM

We propose a laser induced sensitized fluorescence spectrometry for measuring the spontaneous emission branching ratios o?the transitions from the ten levels 5f36d7s7p-7M7, 5f36d7s7p-7L6, 5f37s27p-5K6, 5f26d27s2 - 5L7, 5f46d7s - 7L6, (17,070cm-1)-5L6, 5f26d27s2-5K6, 6d7s7p-7L5, 5f36d7s7p-7K5 and 5f26d27s2-5I5 to the ground state of atomic uranium (UI) for the first time. Their relative oscillator strengths have been measured by means of hollow cathode discharge (HCD) emission spectrometry. The radiative...

A METHOD OF FITTING TO MOSSBAUER SPECTRUM OF EU-151 AND ITS APPLICATION TO EUROPIUM COMPOUNDS

A method of fitting to Mossbauer spectrum of 151Eu has been proposed. The intensities and the positions of all the possible transitions between the sublevels of the ground state and those of the excited state of nucleus with spin I> 3/2 can be considered at one time in fitting to experimental Mossbauer spectra by this method. The method has been used to fit to the experimental Mossbauer spectra of europium orthophosphate crystal and of europium pentaphosphate crystal, and to derive Mossbauer parameters from...

Photodissociation of 1-bromo-2-chloroethane at 266 nm

The photodissociation of CH2BrCH2Cl at 266 nm has been investigated on the universal crossed molecular beam machine. The primary dissociation step leads exclusively to the formation of CH2CH2Cl radicals and Br atoms in the electronic ground state as well as in the spin-orbit excited state, with a branching ratio 2 +/- 1:8 +/- 1. Photofragment total c.m. translational energy distribution P(E-t) has been obtained and about 64% of the available energy is partitioned into translational energy for Br channel and about 28.5% of the available energy is partitioned into translational energy for Br* channel. The anisotropy parameters are determined to be beta(Br*) = 0.8 +/- 0.2 and beta(Br) = -0.6 +/- 0.2, respectively. Some CH2CH2Cl radicals with large internal excitation (corresponding to formation of ground state Br channel) may undergo secondary dissociation to form CH2CH2 +/- Cl. The experimental results are discussed in terms of a model that involves the initial excitation of two repulsive electronic states: one from an parallel transition to the (3)Q(0) state, and the other from a perpendicular transition to the (3)Q(1), (1)Q states. (C) 1999 Elsevier Science B.V. All rights reserved.

Photodissociation of bromobenzene at 266 nm

The photodissociation of C6H5Br at 266 nm has been investigated on the universal crossed molecular beam machine, and time-of-flight spectra as well as the angular distribution of Br atom have been measured. Photofragment translational energy distribution P(E-t) reveals that about 47% of the available energy is partitioned into translational energy. The anisotropy parameter beta at this wavelength is -0.7+/-0.2. From P(E-t) and beta, we deduce that C6H5Br photodissociation is a fast process and the transition dipole moment is almost perpendicular to the C-Br bond. Ab initio calculations have been performed, and the calculated results show that the geometry of the first excited state of bromobenzene has changed apparently compared with that of the ground state. Two kinds of possible fast dissociation mechanism have also been proposed. (C) 1999 American Institute of Physics. [S0021-9606(99)01206-4].

Photodissociation of o-dichlorobenzene at 266 nm

The photodissociation o-dichlorobenzene at 266 nm has been investigated using the universal crossed molecular beam technique. Photofragment translational energy distribution P(E-t) and angular distribution of photofragments have been obtained and it is estimated that 23% of the available energy is assigned to translational energy. The anisotropy parameter is determined to be 0.4. From P(E-t) and beta we deduce that o-C6H4Cl2 photodissociation is a slow process. Ab initio calculation has been performed and it shows that the parent molecule has a larger geometry deformation in its excited states comparing with that of the ground state. The possible dissociation mechanism has also been proposed. (C) 1999 Elsevier Science B.V. All rights reserved.