Synthesis and optical properties of metal-centered dimeric fullerene macromolecules

Dimeric fullerene macromolecules were prepared via the complexation of two fullerenylated 2,2′:6′,2″-terpyridine ligands with Fe(II) and Co(II) ions. The solubility of these macromolecules in some organic solvents allowed both their structural characterization and a study of their optical properties. The electronic absorption and emission of the macromolecules in solution were evaluated; and the results indicated no meaningful ground-state and excited singlet state intramolecular charge transfer interactions. However, the laser flash photolysis results could be explained in terms of the electron transfer quenching of the excited triplet methanofullerene moiety by the center metal–ligand complex in the macromolecules. The optical limiting properties of the macromolecules in solution were also investigated in comparison with those of the ligands for an evaluation of the complexation effects.     

Structural trends of 29Si–1H spin–spin coupling constants across double bond

The calculations of geminal and vicinal ²⁹Si–¹H spin–spin coupling constants across double bond in 15 alkenylmethylsilanes and alkenylchlorosilanes were carried out at the second‐order polarization propagator approach level in a good agreement with experiment. Two structural trends, namely, (i) the geometry of the coupling pathway and (ii) the effect of the electrowithdrawing substituent, have been interpreted in terms of the natural J‐coupling analysis within the framework of the natural bond orbital approach. Thus, the marked difference between cisoidal and transoidal ²⁹Si–¹H spin–spin coupling constants across double bond was accounted for the delocalization contributions including bonding and antibonding Si–C and C–H orbitals, whereas the chlorine effect was explained in terms of the steric contributions including bonding Si–Cl orbitals. Copyright © 2012 John Wiley & Sons, Ltd.     

Size effects in monodomain magnetite based ferrofluids

Ferrofluids based on two types of hybrid particles Fe₃O₄/β-cyclodextrin were prepared: Using monodomain (below 60 nm) magnetite nanoparticles with (A) non-superparamagnetic (non-SPM) behaviour and (B) with superparamagnetic (SPM) behaviour. We found a strong dependence of the hybrid particles’ magnetic properties on their size and homogeneity. In both types of ferrofluids we observed hyperthermia upon applying an ac electromagnetic field with frequency 40 kHz and amplitude 30 kA/m. The maximal ΔТ upon irradiation with duration of about 12 min for the non-SPM particles was 12 °C, while for the SPM ones it was 3.5 °C.     

Line Intensity of R(0) and R(3) of the CH4 2ν3 Band from Diode Laser Spectroscopy

We have determined the spectroscopic parameters that are necessary to describe accurately the R(0) line profile of the CH₄ 2ν₃ band from about 1 Torr to a few hundred Torr of pure CH₄. The intensities determined at each pressure are in overall agreement to better than 0.7%. The R(3) manifold of the same band has also been investigated. Relative positions and absolute intensities of the three transitions composing the triplet have been determined. The intensity distribution inside the triplet is in fair agreement with recent theoretical predictions.     

Demonstration of a Ni-like Kr optical-field-ionization collisional soft x-ray laser at 32.8 nm

We report the first experimental demonstration of a Ni-like optical-field ionization collisional soft x-ray laser. The amplifying medium is generated by focusing a circularly polarized 760 mJ, 30 fs, 10-Hz Ti:sapphire laser beam in a few mm cell filled with krypton. We have measured a gain coefficient of 78 cm(-1) on the 3d(9)4d 1S0-3d(9)4p(1)P1 transition at 32.8 nm, which is here amplified for the first time. This radiation source represents the shortest wavelength optical-field ionization collisional soft x-ray laser ever produced. The influence of the gas pressure and the pumping energy on the lasing output are also presented.     

Measurement and interpretation of the 1-0 band of 14N16O at 1900 cm−1

The wavenumbers of the vibration rotation band lines of ¹⁴N¹⁶O are reported for the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ subbands of the 1-0 transition in the infrared. The full set of spectroscopic constants for this band has been determined by direct approach using the analysis of Zare, Schmeltekopf, Harrop, and Albritton. In addition to the band origin ν₀ and the B, D, H constants for the lower and upper vibrational levels, the following spin-orbit coupling constants have been derived: $\text{A}\text{?}{}_0\text{= 123.02772 ± 0.00011}$ and $\text{A}\text{?}{}_1\text{= 122.78248 ± 0.00011}$ (in cm^?1). Apparent centrifugal corrections to these constants have been determined and the values obtained for them are $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>0</mtext>}}\text{= (0.347573 ± 0.00051) × 10}{}^{\mathrm{?3}}$ and $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>1</mtext>}}\text{= (0.337135 ± 0.00050) × 10}{}^{\mathrm{?3}}\text{cm}{}^{\mathrm{?1}}$. Λ-Type doubling constants evaluated by using both grating and tunable laser data are also reported.     

Calculation of collisional and radiative transition probabilities between excited argon levels

Average radiative transition probabilities for argon atoms have been calculated for transitions between 24 levels in two groups characterized by the atomic core terms ²P_1/2 and ²P_3/2 by using the method of Bates and Damgaard. The results are compared with data in the NBS tables (Wiese et al.) and with those of Katsonis and Drawin. We find satisfactory agreement for the order of magnitude, even for transitions between lower lying levels. Parameters, which appear in Drawin's semiempirical cross-section expressions for electronic excitation of optically allowed and parity-forbidden transitions, are determined with the multipole expansion method proposed by Sobel'man for transitions between the specified levels. Most of these are easily obtained, but the method must be improved for transitions between levels having the same azimuthal quantum number because the summation over the constituent terms does not converge.     

Quantum-chemical study of the interface formed by carboxylic species on TiO<Subscript>2</Subscript> nanoparticles. 1. Nanoparticle surface

The current paper presents results of a quantum-chemical study of the surface structure of nanoparticles of both rutile and anatase crystallographic modifications. Different stages of the surface relaxation are discussed. Water adsorption is considered. The calculations were performed in the spd-basis by using semi-empirical quantum-chemical codes, both sequential and parallel. The results are mainly addressed to the study of the interface formed by titania nanoparticles and a set of carboxylated species, namely, benzoic, bi-isonicotinic acids as well as tris-(2,2′-dcbipyridine) Fe(II) complex placed on the surface of either rutile or anatase polymorphs.This revised version was published online in August 2005 with a corrected issue number.     

Attosecond electron wave packet dynamics in strong laser fields

We use a train of sub-200 attosecond extreme ultraviolet (XUV) pulses with energies just above the ionization threshold in argon to create a train of temporally localized electron wave packets. We study the energy transfer from a strong infrared (IR) laser field to the ionized electrons as a function of the delay between the XUV and IR fields. When the wave packets are born at the zero crossings of the IR field, a significant amount of energy (approximately 20 eV) is transferred from the field to the electrons. This results in dramatically enhanced above-threshold ionization in conditions where the IR field alone does not induce any significant ionization. Because both the energy and duration of the wave packets can be varied independently of the IR laser, they are valuable tools for studying and controlling strong-field processes.