Ionization of aromatic sulfides in nonpolar media: free vs reaction-controlled electron transfer

The primary products of the bimolecular free electron transfer (FET) from aromatic sulfides (PhSCH2Ph, PhSCHPh2, PhSCPh3) to n-butyl chloride radical cations are two radical cation conformers: a dissociative and a metastable one. In analogy with formerly studied donor systems, this result seems to reflect femtosecond oscillations in the ground state of the sulfides such as torsion motions around the Ar-S bond. This motion is accompanied by a marked electron fluctuation within the HOMO (or the n) orbitals. The FET products observed in the nanosecond time scale such as the metastable sulfide radical cations (Ar-S-CR3*+), the dissociation products R3C+; and R3C*, and their (experimentally) nondetectable counterparts Ar-S* as well as Ar-S+ can be understood with the simplified assumption of two extreme conformations, namely a planar and a twisted donor molecule. Using mediator radical cations (benzene, butylbenzene, biphenyl), the stepwise reduction of the free energy of the electron transfer from -DeltaH = 2.5 to 相似文献   

Structural investigation of asymmetrical dimer radical cation system (H2O-H2S)+: proton-transferred or hemi-bonded?

Ab initio molecular orbital and hybrid density functional methods have been employed to characterize the structure and bonding of (H2O-H2S)+, an asymmetrical dimer radical cation system. A comparison has been made between the two-center three-electron (2c-3e) hemi-bonded system and the proton-transferred hydrogen-bonded systems of (H2O-H2S)+. Geometry optimization of these systems was carried out using unrestricted Hartree Fock (HF), density functional theory with different functionals, and second-order M?ller-Plesset perturbation (MP2) methods with 6-311++G(d,p) basis set. Hessian calculations have been done at the same level to check the nature of the equilibrium geometry. Energy data were further improved by calculating basis set superposition error for the structures optimized through MP2/6-311++G(d,p) calculations. The calculated results show that the dimer radical cation structure with H2O as proton acceptor is more stable than those structures in which H2O acts as a proton donor or the 2c-3e hemi-bonded (H2O thereforeSH2)+ system. This stability trend has been further confirmed by more accurate G3, G3B3, and CCSD(T) methods. On the basis of the present calculated results, the structure of H4OS+ can best be described as a hydrogen-bonded complex of H3O+ and SH with H2O as a proton acceptor. It is in contrast to the structure of neutral (H2O...H2S) dimer where H2O acts as a proton donor. The present work has been able to resolve the ambiguity in the nature of bonding between H2O and H2S in (H2O-H2S)+ asymmetrical dimer radical cation.     

Ionization of aniline and its N-methyl and N-phenyl substituted derivatives by (free) electron transfer to n-butyl chloride parent radical cations

The electron transfer from aniline and its N-methyl as well as N-phenyl substituted derivatives (N-methylaniline, N,N-dimethylaniline, diphenylamine, triphenylamine) to parent solvent radical cations was studied by electron pulse radiolysis in n-butyl chloride solution. The ionization results in the case of aniline (ArNH2) and the secondary aromatic amines (Ar2NH, Ar(Me)NH) in the synchronous and direct formation of amine radical cations, as well as aminyl radicals, in comparable amounts. Subsequently, ArNH2*+ deprotonates in a delayed reaction with the present nucleophile Cl-, and forms further ArNH*. In contrast, tertiary aromatic amines such as triphenylamine and dimethylaniline yield primarily the corresponding amine radical cations Ar3N*+ or Ar(Me2)N*+, only. The persistent Ar3N*+ forms a charge transfer complex (dimer) with the parent amine molecule, whereas Ar(Me2)N*+ deprotonates to carbon-centered radicals Ar(Me)NCH2*.     

Optical ratchets with discrete cavity solitons

We propose a setup to observe soliton ratchet effects using discrete cavity solitons in a 1D array of coupled waveguide optical resonators. The net motion of solitons can be generated by an adiabatic shaking of the holding beam with zero average inclination angle. The resulting soliton velocity can be controlled by different parameters of the holding beam.     

The alpha--> gamma transition in Ce: a theoretical view from optical spectroscopy

Using a novel approach to calculate optical properties of strongly correlated systems, we address the old question of the physical origin of the alpha--> gamma transition in Ce. We find that the Kondo collapse model, involving both the f and the spd electrons, describes the optical data better than a Mott transition picture involving the f electrons only. Our results compare well with existing experiments on thin films. We predict the full temperature dependence of the optical spectra and find the development of a hybridization pseudogap in the vicinity of the alpha--> gamma phase transition.     

Quantum subdiffusion with two- and three-body interactions

We study the dynamics of a few-quantum-particle cloud in the presence of two- and three-body interactions in weakly disordered one-dimensional lattices. The interaction is dramatically enhancing the Anderson localization length ξ ₁ of noninteracting particles. We launch compact wave packets and show that few-body interactions lead to transient subdiffusion of wave packets, m ₂ ~ t ^α , α< 1, on length scales beyond ξ ₁. The subdiffusion exponent is independent of the number of particles. Two-body interactions yield α ≈ 0.5 for two and three particles, while three-body interactions decrease it to α ≈ 0.2. The tails of expanding wave packets exhibit exponential localization with a slowly decreasing exponent. We relate our results to subdiffusion in nonlinear random lattices, and to results on restricted diffusion in high-dimensional spaces like e.g. on comb lattices.     

A new sample environment for cryogenic nuclear resonance scattering experiments on single crystals and microsamples at P01, PETRA III

In order to carry out orientation dependent nuclear resonance scattering (NRS) experiments on small single crystals of e.g. iron proteins and/or chemical complexes but also on surfaces and other micrometer-sized samples a 2-circle goniometer including sample positioning optics has been installed at beamline P01, PETRA III, DESY, Hamburg. This sample environment is now available for all users of this beamline. Sample cooling is performed with a cryogenic gas stream which allows NRS measurements in the temperature range from 80 up to 400 K. In a first test this new sample environment has been used in order to investigate the orientation dependence of the nuclear inelastic scattering (NIS) signature of (i) a dinuclear iron(II) spin crossover (SCO) system and (ii) a hydrogen peroxide treated metmyoglobin single crystal.     

Light scattering by a finite obstacle and fano resonances

The conditions for observing Fano resonances at elastic light scattering by a single finite-size obstacle are discussed. General arguments are illustrated by consideration of the scattering by a small (relative to the incident light wavelength) spherical obstacle based upon the exact Mie solution of the diffraction problem. The most attention is paid to recently discovered anomalous scattering. An exactly solvable one-dimentional discrete model with nonlocal coupling for simulating diffraction in wave scattering in systems with reduced spatial dimensionality is also introduced and analyzed. Deep connections between the resonances in the continuous and discrete systems are revealed.     

An enormous vibrational motion: the gas-phase structure of dimethyl-bis(methoxyethynyl) germanium

The structure of dimethyl-bis(methoxyethynyl) germanium has been determined in the gas phase by electron diffraction utilising flexible restraints from quantum chemical calculations. Theoretical methods (B3LYP/6-311+G* and MP2/6-311+G*) predict a low barrier to rotation of the methoxy groups in the molecule in addition to low-frequency vibrations of the long ethynyl chains. In the equilibrium structure the Ge-C[triple bond]C angles of the two methoxyethynyl fragments in the molecule are computed to deviate by up to 4 degrees from the linear arrangement. As a consequence of low-frequency large-amplitude vibrational motion the experimental structure of these fragments without applying vibrational corrections deviates considerably from linearity, while the structure corrected for vibrational effects using the harmonic approximation and taking into account a non-linear transformation between internal and Cartesian coordinates (r(h1)) shows closer agreement with theory. The main experimental structural parameters of dimethyl-bis(methoxyethynyl) germanium (r(h1)) are: r(Ge-C)(mean), 192.5(1) pm; DeltaGeC =r(Ge-C(methyl))-r(Ge-C(ethynyl)), 4.5(5) pm, r(C[triple bond]C)(mean), 122.8(2) pm; r(C-O)(mean), 138.9(3) pm; DeltaCO =r(C(methyl)-O)-r(C(ethynyl)-O), 14.5(2) pm, r(C-H)(mean), 109.1(4) pm; [angle](X-C-H)(mean)(X = Ge,O), 109(1) degree; [angle]C(ethynyl)-Ge-C(ethynyl), 108.1(4) degree; [angle]C(methyl)-Ge-C(methyl), 113.4(5) degree; [angle]Ge-C[triple bond]C, 163(1) degree; [angle]C[triple bond]C-O, 176(2) degree; [angle]C-O-C, 115.2(6) degree; methoxy group torsion, tau, 36(9) degree from the position in which the C-O bond eclipses the further Ge-C(ethynyl) bond.