Spin charge carrier dynamics in poly(bis-alkylthioacetylene)

Initial and laser-irradiated poly(bis-alkylthioacetylene) (PATAC) samples were investigated by electron paramagnetic resonance (EPR) at X-band (9.6 GHz), Q-band (37 GHz), and D-band (140 GHz) in a wide temperature range. Two types of paramagnetic centers were proved to exist in laser-modified polymer, namely, localized and mobile polarons with the concentration ratio and susceptibility depending on the irradiation dose and temperature. Superslow torsion motion of the polymer chains was studied by the saturation transfer method at D-band EPR. Additional information on the polymer chain segment dynamics was obtained by the spin probe method at X-band EPR. Spin-spin and spin-lattice relaxation times were measured separately by the steady-state saturation method at D-band EPR. Intrachain and interchain spin diffusion coefficients and conductivity arising from the polaron dynamics were calculated. It was shown that the polaron dynamics in laser-modified polymer is affected by the spin-spin interaction. The interchain charge transfer is stimulated by torsion motion of the polymer chains, whereas the total conductivity of irradiated PATAC is determined mainly by the dynamic of diamagnetic charge carriers. Magnetic, relaxation and dynamics parameters of PATAC were also shown to change during polymer storage.     

Spin relaxation studies on conducting poly(tetrathiafulvalene)

Magnetic parameters and the relaxation behavior of paramagnetic centers in an iodine-doped poly(tetrathiafulvalene) semiconductor with a d.c. conductivity of 10^?5 S·cm^?1 have been studied using mainly the 2 mm waveband EPR technique in the temperature range of 110–270 K. The EPR line shape analysis confirms the existence of immobile radicals pinne on short polymer chains and mobile polarons with different relaxation parameters in slightly doped poly(tetrathiafulvalene). The temperature dependences of electron spin-lattice and spin-spin relaxation times of paramagnetic centers of both types have been determined independently using the saturation method at the operation frequency ν _e = 140 GHz. An anisotropic slow libration of immobile polarons with an activation energy of 0.02 eV have been registered for the first time using the saturation transfer EPR method. The temperature dependences of intrachain diffusion and interchain hopping rates in poly(tetrathiafulvalene) are determined from theT ₁ andT ₂ EPR data. The interchain spin dynamics is shown to correlate with libration of polarons trapped on polymer chains and is in good agreement with a hopping charge transport mechanism.     

EPR Studies of DOPA–Melanin Complexes with Netilmicin and Cu(II) at Temperatures in the Range of 105–300?K

The application of electron paramagnetic resonance (EPR) spectroscopy in pharmacy of melanin complexes with netilmicin and Cu(II) was presented. The continuous microwave saturation of EPR spectra of DOPA–melanin and the complexes was performed. EPR spectra were measured on an X-band (9.3?GHz) spectrometer at temperatures in the range of 105–300?K. Paramagnetic copper ions decrease the intensity of the EPR lines of melanin’s free radicals. It was found that fast spin–lattice relaxation characterizes DOPA–melanin–Cu(II) complexes. Slow spin–lattice relaxation processes exist in melanin’s paramagnetic centers of DOPA–melanin and DOPA–melanin–netilmicin, [DOPA–melanin–netilmicin]–Cu(II), [DOPA–melanin–Cu(II)]–netilmicin complexes. Spin–lattice relaxation processes are faster at higher temperatures. The homogeneous broadening of EPR lines for melanin complexes was observed. The practical consequences of differences between paramagnetic properties of melanin complexes with netilmicin and the complexes with Cu(II) were discussed.     

Study of Stable L-Alanine Radicals by W-Band EPR Spectroscopy

Stable L-alanine radicals, SAR1 and SAR2, induced by γ-irradiation of the L-alanine crystal have been investigated by electron paramagnetic resonance (EPR) technique at W-band (94 GHz) frequency. The study provides assignment of radical centers detected by continuous-wave EPR, saturation transfer mode and echo-detected field-swept EPR at W-band frequencies. The phase memory time, T _m, which was measured simultaneously at X-band (9.5 GHz) and W-band frequencies for different spectral components has been employed to estimate rotation correlation times of CH₃ protons and an effective correlation time related to the local dynamics of the entire SAR1 center at room temperature.     

Analysis of the optical properties of poly(3‐octylthiophene) partially dedoped

In this work, poly(3‐octylthiophene) (P3OT) films were synthesized electrochemically in non‐aqueous media through the oxidation of the monomer, (3‐octylthiophene), using a standard three‐electrode cell in acetonitrile with 0.05 mol L^?1 LiClO₄ or 0.05 mol L^?1 Et₄NBF₄. The polymeric films were deposited on fluorine tin oxide (FTO). The partial dedoping was obtained in NH₄OH solution, providing a good chemical stability of the formed material. The films obtained through this method have been characterized by Fourier‐transform infrared spectroscopy (FT‐IR), electron paramagnetic resonance (EPR), UV–Vis absorption, and photoluminescence (PL) spectroscopy. The FT‐IR and EPR spectra together gave the results that led to characterization of two structures (pristine and non‐pristine forms of thiophene rings) while forming the P3OT polymer chain. These results were associated with the stabilization of pristine chains and mixed chains (non‐pristine structures) in the polymeric film. Their bands in the PL spectra are wide and asymmetric and their adjustments by Gaussian functions was necessary; this was the main indication that there are two distinct contributions to the emission spectra. These two contributions are attributed to the emission by mixed chains (Gaussian centered at higher energy) and by pristine chains (Gaussian of lower energy) present in the formed polymeric material. Copyright © 2010 John Wiley & Sons, Ltd.     

High-field EPR studies on polymer film formation from colloidal dispersions

High-field EPR on nitroxide spin probes is applied to characterize the dynamics of small additive molecules and surfactants in polymer films obtained from colloidal dispersions. Due to the increased width of the spectra and the smaller influence of hyperfine-dependent relaxation on the spectral lineshape at W band (94 GHz) compared to X band (9.6 GHz), it is possible to measure subnanosecond rotational correlation times for the isotropic motion of the unpolar spin probe TEMPO in the free volume of poly(acrylate) films. Likewise, the anisotropies of the rotational diffusion tensors of a surfactant and a small ionic additive molecule in poly(fluoroacrylate) films can be determined with better confidence at W band. From these anisotropies it is concluded that the surfactant aggregates exhibit low molecular order, whereas the ionic additives are strongly attached to immobilized ionic clusters. High-field EPR lineshapes at W band are also found to be more sensitive to slow motions on a microsecond time scale than X-band EPR lineshapes. The design of a Fabry-Pérot resonator for measurements on polymer films is discussed and its sensitivity is demonstrated on a wet polymer film with a thickness of 160 μm.     

Broad band dielectric behaviour of plasticized PEO-based solid polymer electrolytes

The conductivity and dielectric response of poly(ethylene oxide) (PEO) based plasticized polymer electrolyte systems were studied in the broad frequency range from 5 Hz to 1.8 GHz and in the temperature range from 248 K to 353 K. Propylene carbonate (PC) and ethylene carbonate (EC) were used as conventional plasticizers while poly(perfluorinated ethylene methylene oxide) (M03) was used as a new type of plasticizer. PEO-LiN(CF₃SO₂)₂ plasticized with M03 shows high enough conductivity values to be used as electrolyte in rechargeable lithium polymer batteries. At high frequency a dielectric relaxation is observed for pure PEO as well as for the salt containing systems in the GHz region that is assumed to be due to segmental motion of the polymer chains. In the salt containing systems, this relaxation is shifted to lower frequencies relative to that of pure PEO, this is attributed to transient cross-linking. However, at lower frequencies another dielectric response peak was detected in all samples containing salts. The effect of the plasticizer on this relaxation is complex. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Physics of Polymers at the Italian High-Field EPR Facility: Heterogeneities and Fast Dynamics

The reorientation of the paramagnetic molecule 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) dissolved in glassy polystyrene (PS) is studied by electron paramagnetic resonance (EPR) spectroscopy in a wide range of Larmor frequencies (9–285 GHz). High-field EPR reveals that TEMPO rotates by small angular steps with a distribution of correlation times and is able to detect the onset of fast motion of PS. Differently, X-band EPR shows that TEMPO undergoes a large-angle reorientation with virtually no distribution of correlation times and largely misses the fast dynamics of PS. A unified view is proposed. Authors' address: Dino Leporini, Dipartimento di Fisica "Enrico Fermi", Università di Pisa, Largo Pontecorvo 3, Pisa 56127, Italy     

Mechanism of relaxation enhancement of spin labels in membranes by paramagnetic ion salts: dependence on 3d and 4f ions and on the anions

Progressive saturation EPR measurements and EPR linewidth determinations have been performed on spin-labeled lipids in fluid phospholipid bilayer membranes to elucidate the mechanisms of relaxation enhancement by different paramagnetic ion salts. Such paramagnetic relaxation agents are widely used for structural EPR studies in biological systems, particularly with membranes. Metal ions of the 3d and 4f series were used as their chloride, sulfate, and perchlorate salts. For a given anion, the efficiency of relaxation enhancement is in the order Mn(2+) > or = Cu(2+) > Ni(2+) > Co(2+) approximately Dy(3+). A pronounced dependence of the paramagnetic relaxation enhancement on the anion is found in the order ClO(-)(4) > Cl(-) > SO(2-)(4). This is in the order of the octanol partition coefficients multiplied by spin exchange rate constants that were determined for the different paramagnetic salts in methanol. Detailed studies coupled with theoretical estimates reveal that, for the chlorides and perchlorates of Ni(2+) (and Co(2+)), the relaxation enhancements are dominated by Heisenberg spin exchange interactions with paramagnetic ions dissolved in fluid membranes. The dependence on membrane composition of the relaxation enhancement by intramembrane Heisenberg exchange indicates that the diffusion of the ions within the membrane takes place via water-filled defects. For the corresponding Cu(2+) salts, additional relaxation enhancements arise from dipolar interactions with ions within the membrane. For the case of Mn(2+) salts, static dipolar interactions with paramagnetic ions in the aqueous phase also make a further appreciable contribution to the spin-label relaxation enhancement. On this basis, different paramagnetic agents may be chosen to optimize sensitivity to different structurally correlated interactions. These results therefore will aid further spin-label EPR studies in structural biology.     

Investigation of MWS Relaxation in Nylon 1010 using Dielectric Relaxation Spectroscopy

Maxwell–Wagner–Sillars (MWS) relaxation in nylon 1010, arising from charge carriers accumulated at the interphase between amorphous and crystalline regions, has been investigated by means of dielectric relaxation spectra. In the frequency spectra of nylon 1010, dielectric permittivity showed high values at low frequencies originating from charge carrier movement. For the MWS relaxation, the dielectric strength was independent of temperature. The results revealed that there is a transition temperature, located between 110 and 120°C, resulting in the separation of two different charge carrier movement mechanisms. Below and above this transition temperature, the temperature dependence of the MWS relaxation time follows the Vogel–Tammann–Fulcher type, showing that the charge carrier transport is governed by the motion of the polymer chains. The change of charge carrier movement mechanisms is due to the onset of polymer chain motion in the interphase.     

Estimation of higher-order magnetic spin interactions of Fe(III) and Gd(III) ions doped in α-alumina powder with multifrequency EPR

Fe(III) and Gd(III) ions in α-alumina (A1₂O₃) exhibit spin states ofS = 5/2 andS = 7/2 respectively. The magnitude of the zero-field interaction (ZFI) (D = 0.10?0.15 cm^?1) gives rise to an inter Kramers doublet splitting in the same order of magnitude as the X-band electron paramagnetic resonance (EPR) quantum (0.3 cm^?1). It is demonstrated that through a careful step-by-step analysis and spectral simulation of EPR spectra taken at D-band (130 GHz), Q-band (35 GHz), and X-band (9 GHz) at room temperature, the (relative) sign and magnitude of the ZFI parameters, b ₂ ⁰ , b ₄ ⁰ , and b ₄ ³ , can be reliably estimated.     

Comparison of Continuous Wave, Spin Echo, and Rapid Scan EPR of Irradiated Fused Quartz

The E' defect in irradiated fused quartz has spin lattice relaxation times (T(1)) about 100 to 300 μs and spin-spin relaxation times (T(2)) up to about 200 μs, depending on the concentration of defects and other species in the sample. These long relaxation times make it difficult to record an unsaturated continuous wave (CW) electron paramagnetic resonance (EPR) signal that is free of passage effects. Signals measured at X-band (~9.5 GHz) by three EPR methods: conventional slow-scan field modulated EPR, rapid scan EPR, and pulsed EPR, were compared. To acquire spectra with comparable signal-to-noise, both pulsed and rapid scan EPR require less time than conventional CW EPR. Rapid scan spectroscopy does not require the high power amplifiers that are needed for pulsed EPR. The pulsed spectra, and rapid scan spectra obtained by deconvolution of the experimental data, are free of passage effects.     

High intrachain hole mobility on molecular wires of ladder-type poly(p-phenylenes)

We have studied the high-frequency (34 GHz) mobility of positive charge carriers on isolated ladder-type polymer chains in dilute solution. We find that the high-frequency mobility is limited by the chain ends on chains as long as 35 monomers. The intrachain motion of charge carriers can be described by one-dimensional diffusion between infinitely high reflecting barriers, representing the chain ends. Our data indicate that the intrachain mobility for ladder-type polymer chains is close to 600 cm(2)/V s. With this high mobility the ladder-type polymer is a promising candidate for future use as an interconnecting wire in molecular electronics.     

13C spin-lattice relaxation in natural diamond: Zeeman relaxation at 4.7 T and 300 K due to fixed paramagnetic nitrogen defects

13C spin-lattice relaxation times in the laboratory frame, ranging from 1.4 to 36 h, have been measured on a suite of five natural type Ia and Ib diamonds at 4.7 T and 300 K. Each of the diamonds contains two types of fixed paramagnetic centers with overlapping inhomogeneous electron paramagnetic resonance (EPR) lines. EPR techniques have been employed to identify these defects and to determine their concentrations and relaxation times at X-band. Spin-lattice relaxation behavior of 13C in diamonds containing paramagnetic P1, P2, N2. and N3 centers are discussed. Depending on the paramagnetic impurity types and concentrations present in each diamond, three different nuclear spin-lattice relaxation (SLR) paths exist, namely that due to electron SLR mechanisms and two types of three-spin processes (TSPs). The one three-spin process (TSP1) involves a simultaneous transition of two electron spins belonging to the same hyperfine EPR line and a flip of a 13C spin, while the other process (TSP2) involves two electron spins belonging to different hyperfine EPR lines and a 13C spin. It is shown that the thermal contact between the 13C nuclear Zeeman and electron dipole-dipole interaction reservoirs is field dependent, thus forming a bottleneck in the 13C relaxation path due to TSP1 at high magnetic fields.     

Spin Localization in Poly(3-Dodecylthiophen)/PCBM Composite

Charge carriers photoinduced in poly(3-dodecylthiophene)/([6,6]-phenyl-C₆₁-butanoic acid methyl ester) (P3DDT/PCBM) by photons with the energy of 1.88–2.75 eV were investigated by X-band light-induced electron paramagnetic resonance (LEPR). LEPR spectra were attributed to non-interacting polarons and methanofullerene anion radicals with different magnetic and relaxation parameters. A part of these charge carriers are trapped in a polymer matrix. Paramagnetic susceptibility and spin–spin relaxation of mobile charge carriers were shown to follow the activation law.     

Multifrequency time-resolved EPR (9.5GHz and 95GHz) on covalently linked porphyrin-quinone model systems for photosynthetic electron transfer: effect of molecular dynamics on electron spin polarization

Covalently linked porphyrin–quinone model systems for photosynthetic electron transfer were examined by using time-resolved electron paramagnetic resonance (TREPR) at intermediate magnetic field and microwave frequency (0.34T/9.5GHz, X-band) and high field and frequency (3.4T/95GHz, W-band). The paramagnetic transients studied were the light-induced spin-correlated radical pair states of the donor–acceptor complex in polar solvents below the melting point and in the soft glass phase of a liquid crystal. It is shown that the systems form strongly exchange-coupled radical pairs, whose TREPR lineshapes are determined mainly by fast electron recombination together with both spin–lattice relaxation and modulation of the exchange interaction. Below the melting point the spin–lattice relaxation rate naturally slows down, but that of the spin on the quinone site is still of the order of 10⁶ s^-1. Most probably this is due to contributions from spin–rotation interaction, and dependent on the molecular orientation with respect to the magnetic field. This relaxation anisotropy is related to anisotropic motion of the quinone site in the solvent cage. The results allow conclusions to be drawn concerning the molecular dynamics and flexibility of the systems. To yield long-lived radical pair states that would mimic photosynthetic electron transfer, the two mechanisms described, modulation of exchange and spin–rotation interactions, have to be suppressed by reducing the molecular flexibility of the complex.     

EPR Spectroscopy of Impurity Thulium Ions in Yttrium Orthosilicate Single Crystals

The frequency-field and orientation dependences of the electron paramagnetic resonance (EPR) spectra are measured for impurity Tm³⁺ ions in yttrium orthosilicate (Y₂SiO₅) single crystals by stationary EPR spectroscopy in the frequency range of 50–100 GHz at 4.2 K. The position of the impurity ion in the crystal lattice and its magnetic characteristics are determined. The temperature dependences of the spin–lattice and phase relaxation times are measured by pulse EPR methods in the temperature range of 5–15 K and the high efficiency of the direct single-phonon mechanism of spin–lattice relaxation is established. This greatly shortens the spin–lattice relaxation time at low temperatures and makes impurity Tm³⁺ ions in Y₂SiO₅ a promising basis for the implementation of high-speed quantum memory based on rare-earth ions in dielectric crystals.     

High-frequency EPR of Tb<Superscript>3+</Superscript>-doped KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystal

High-frequency electron paramagnetic resonance (EPR) spectra of the KPb₂Cl₅:Tb³⁺ crystal have been investigated. Three types of spectra were observed in the frequency range of 74–200 GHz. The most intensive spectrum with the resolved hyperfine structure corresponded to transitions between sublevels of the¹⁵⁹Tb³⁺ ground quasi-doublet with the zero-field splitting (ZFS) close to 48 GHz. Experimental results were analyzed by the exchange charge model of the crystal field affecting terbium ions in low-symmetry Pb²⁺ positions with the chlorine sevenfold coordination and the charge compensating vacancy in the nearest potassium site. The calculated values ofg-factors and ZFS were in agreement with the experimental data. The nature of a broad EPR line with ZFS of about 180 GHz and of additional weak EPR lines observed as satellites of the main Tb³⁺ lines was discussed.     

AC conductivity and relaxation behavior in ion conducting polymer nanocomposite

We report the ac conductivity and relaxation behavior analysis for a heterogeneous polymer–clay nanocomposite (PNC) having composition (polyacrylonitrile)₈LiCF₃SO₃ + x wt.% dodecylamine modified montmorillonite. Charge transport behavior in an ionically conducting PNC has been analyzed systematically and correlated with the macroscopic parameters like polymer glass transition temperature and available free mobile charge carriers. Intercalation of cation coordinated polymer into the nanometric clay channels has been confirmed by high-resolution transmission electron microscopy. The electrical properties of the intercalated PNC films have been studied using complex impedance/admittance spectroscopy. Excellent correlation of relaxation behavior with polymer glass transition temperature (T _g) confirmed the objectives of the work. An analysis of dielectric relaxation indicates that PNC films are lossy when compared with polymer–salt film. This result is a direct outcome of faster ion dynamics leading to strong electrode polarization effect due to the accumulation of charge carriers at the interface.     

Angle-selective measurements of spin soliton in ladder polydiacetylene by pulsed 94 GHz EPR

Angle-selection experiments of a spin soliton in randomly oriented ladder polydiacetylene were carried out by pulsed electron paramagnetic resonance (EPR) at W-band. EPR measurement using 94 GHz microwaves increased the difference in the resonance field due tog anisotropy of the spin soliton to allow the orientation dependence of transient nutation, electron nuclear double resonance (ENDOR) and spin relaxations to be investigated. The shape of theg anisotropy-resolved nutation spectrum was discussed on the basis of the EPR transition moments and the differences between spin relaxation times. Reliable assignments of hyperfine couplings to the β protons (H_β) of the alkyl side chains were achieved with the support of W-band ENDOR measurements. No significant orientational dependence in theT ₁ andT ₂ processes was found in terms of isotropy of the H_β-hyperfine interaction.