Internal energy content of n-butylbenzene, bromobenzene, iodobenzene and aniline molecular ions generated by two-photon ionization at 266 nm. A photodissociation study

A technique to investigate photodissociation kinetics on a nanosecond time scale has been devised for molecular ions generated by multiphoton ionization (MPI) using mass-analyzed ion kinetic energy spectrometry. The branching ratio or rate constant has been determined for the photodissociation of the n-butylbenzene, bromobenzene, iodobenzene, and aniline molecular ions generated by MPI at 266 nm. The ion internal energies have been estimated by comparing the measured kinetic data with the previous energy dependence data. The analysis has shown that only those molecular ions generated by two-photon ionization contribute to the photodissociation signals. Around half of the available energy has been found to remain as molecular ion internal energy in the two-photon ionization process. Copyright 1999 John Wiley & Sons, Ltd.     

Characterization of fullerenes using positrons

Positron distributions and lifetimes in the K_xC₆₀ crystals for x=0, 3, 4, 6 have been calculated using the superposed-atom model and the numerical relaxation technique. It is revealed that positrons are distributed predominantly at the octahedral interstices in the fcc lattice of pure C₆₀. The distributions and lifetimes of positrons are significantly changed by potassium doping. In the fcc K₃C₆₀, the positron density shows its maxima in the interstitial region between the octahedral and tetrahedral interstices and has some amplitude in the inner space of the C₆₀ molecules. In contrast to this, positrons are distributed one-dimensionally along the [001] direction in the bct K₄C₆₀ while positrons are nearly localized into the C₆₀ molecules in the bcc K₆C₆₀.     

Conducting dimerized cobalt complexes with tetrathiafulvalene dithiolate ligands

To obtain novel single-component molecular metals, we attempted to synthesize several cobalt complexes coordinated by TTF (tetrathiafulvalene)-type dithiolate ligands. We succeeded in the syntheses and structure determinations of ((n)Bu(4)N)(2)[Co(chdt)(2)](2) (1), ((n)Bu(4)N)(2)[Co(dmdt)(2)](2) (2), [Co(dmdt)(2)](2) (3), and [Co(dt)(2)](2) (4) (chdt = cyclohexeno-TTF-dithiolate, dmdt = dimethyl-TTF-dithiolate, and dt = TTF-dithiolate). Structure analyses of complexes 1-4 revealed that two monomeric [Co(ligand)2]- or [Co(ligand)(2)](0) units are connected by two Co-S bonds resulting in dimeric [Co(ligand)(2)](2)(2-) or [Co(ligand)(2)](2) molecules. Complex 1 has a cation-anion-intermingled structure and exhibited Curie-Weiss magnetic behavior with a large Curie constant (C = 2.02 K x emu x mol(-1)) and weak antiferromagnetic interactions (theta = -8.3 K). Complex 2 also has a cation-anion-intermingled structure. However, the dimeric molecules are completely isolated by cations. Complexes 3 and 4 are single-component molecular crystals. The molecules of complex 3 form two-dimensional molecular stacking layers and exhibit a room-temperature conductivity of sigmart = 1.2 x 10(-2) S.cm(-1) and an activation energy of E(a) = 85 meV. The magnetic behavior is almost consistent with Curie-Weiss law, where the Curie constant and Weiss temperature are 8.7 x 10(-2) K x emu x mol(-1) and -0.85 K, respectively. Complex 4 has a rare chair form of the dimeric structure. The electrical conductivity was fairly large (sigmart = 19 S.cm(-1)), and its temperature dependence was very small (sigma(0.55K)/sigma(rt) = ca. 1:10), although the measurements were performed on the compressed pellet sample. Complex 4 showed an almost constant paramagnetic susceptibility (chi(300) (K) = 3.5 x 10(-4) emu x mol(-1)) from 300 to 50 K. The band structure calculation of complex 4 suggested the metallic nature of the system. Complex 4 is a novel single-component molecular conductor with a dimeric molecular structure and essentially metallic properties down to very low temperatures.     

Clifford Fourier Transformation and Uncertainty Principle for the Clifford Geometric Algebra Cl 3,0

First, the basic concept of the vector derivative in geometric algebra is introduced. Second, beginning with the Fourier transform on a scalar function we generalize to a real Fourier transform on Clifford multivector-valued functions Third, we show a set of important properties of the Clifford Fourier transform on Cl_3,0 such as differentiation properties, and the Plancherel theorem. Finally, we apply the Clifford Fourier transform properties for proving an uncertainty principle for Cl_3,0 multivector functions.     

Wave shape of de Haas-van Alphen oscillations and effective mass in the two-dimensional organic conductor α-(BEDT-TTF)2KHg(SCN)4

De Haas-van Alphen (dHvA) oscillations in the two dimensional organic conductor α-(BEDT-TTF)₂KHg(SCN)₄ have been measured by a canti-lever technique at high magnetic fields up to 30 T. The wave shape of the dHvA oscillations undergoes a drastic change around the transition field B_K (24 T). The effective mass shifts 1.5 m₀ in the density wave phase (B<B_K) to 1.65 m₀ in the normal metallic phase (B>B_K). Based on the simulation, we have determined that the primary cause of the characteristic field dependence of the wave shape is the change in the effective mass.     

Ambient-pressure superconductivity at 8 K in the organic conductor β-(BEDT-TTF)2I3

We report that the superconductivity with the onset temperature as high as 8 K in the organic conductor of β-(BEDT-TTF)₂I₃, which was achieved by an application of a soft pressure, i.e. 1.3 kb, remains stable with even higher transition temperature after a subsequent release of pressure to the ambient pressure. Correspondingly, higher values of the upper critical field, H_c2, are observed. (H_c2 > 20 k0e at 2 K along the c¹-axis.)     

Communication: Manipulating the singlet-triplet equilibrium in organic biradical materials

We investigated the tunability of the singlet-triplet equilibrium population in the organic biradical 1,4-phenylenedinitrene via magneto-optical spectroscopy. A rich magnetochromic response occurs because applied field increases the concentration of the triplet state species, which has a unique optical signature by comparison with the singlet biradical and the precursor molecule. A Curie-like analysis of the magneto-optical properties allows us to extract the spin gap, which is smaller than previously supposed. These measurements establish the value of local-probe photophysical techniques for magnetic property determination in open-shell systems such as biradicals where a traditional electron paramagnetic resonance Curie law analysis has intrinsic limitations.