A quantum many body model for the embedded electron spin decoherence in organic solids.

We present a generalized nuclear spin bath model for embedded electron spin decoherence in organic solids at low temperatures, which takes the crucial influence from hindered methyl group rotation tunneling into account. This new, quantum many body model, after resolved using the cluster correlation expansion method, predicts the decoherence profiles directly from the proton relative position and methyl group tunneling splitting inputs. Decoherence profiles from this model explain adequately the influence from both strongly and weakly hindered methyl groups to embedded electron spin decoherence: The former accelerates decoherence by increasing the nearest neighbor nuclear spin coupling, while the latter enhances coherence through a novel confinement like' mechanism, in which the very strong nuclear spin coupling from the tunneling splitting term suppresses those protons on the methyl rotors from participating in the bath dynamics.

Modulation sidebands spectra within inhomogeneous CW-EPR line detected by double modulation EPR spectroscopy.

Conventional modulation spectrum, MS, in continuous wave electron paramagnetic resonance, CW-EPR, is produced by applying longitudinal radiofrequency (RF) fields with the frequencies, ω, which exceeds the linewidth, 2πδ, of a single spectral line given in frequency units. The second longitudinal RF field with frequency, ω, is employed to produce double modulation spectrum, DMS. In this work DMS are presented as a specific type of MS which can be produced from an ordinary homogenous line.

Matrix material structure dependence of the embedded electron spin decoherence.

In this article, we present the novel application of the nuclear spin bath model and the cluster correlation expansion method on studying the matrix material structure via embedded electron spin decoherence. Profiles of embedded electron spin decoherence under the Carr-Purcell-Meiboom-Gill dynamical decoupling pulse series in a model system for organic solids (malonic acid) are calculated for different structures. Resulting decay profiles exhibit a strong correlation to the variations of an adjacent proton environment among them.

Enhanced accuracy of the microwave field strength measurement in a CW-EPR by pulsed modulation technique.

The microwave magnetic field strength, B, in the cavity of a conventional continuous wave electron paramagnetic resonance, CW-EPR, spectrometer was measured by employing modulation sidebands, MS, in the EPR spectrum. MS spectrum in CW-EPR is produced by applying the modulation frequency, ω, which exceeds the linewidth, δB, given in frequency units. An amplitude-modulated CW-EPR, AM-CW-EPR, was selected as detection method.

Insight into the template effect of vesicles on the laccase-catalyzed oligomerization of N-phenyl-1,4-phenylenediamine from Raman spectroscopy and cyclic voltammetry measurements.

We report about the first Raman spectroscopy study of a vesicle-assisted enzyme-catalyzed oligomerization reaction. The aniline dimer N-phenyl-1,4-phenylenediamine (= p-aminodiphenylamine, PADPA) was oxidized and oligomerized with Trametes versicolor laccase and dissolved O2 in the presence of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) vesicles (80-100 nm diameter) as templates. The conversion of PADPA into oligomeric products, poly(PADPA), was monitored during the reaction by in situ Raman spectroscopy.

Magnetic order in a novel 3D oxalate-based coordination polymer {[Cu(bpy)3][Mn2(C2O4)3]·H2O}n.

A heterometallic coordination polymer {[Cu(bpy)3][Mn2(C2O4)3]·H2O}n (1; bpy = 2,2'-bipyridine) was synthesized using a building-block approach and characterized by IR spectroscopy, single-crystal X-ray diffraction, magnetization measurement, and X-band ESR spectroscopy both on a single crystal and a polycrystalline sample. The molecular structure of 1 is made of a three-dimensional (3D) anionic network [Mn2(C2O4)3]n(2n-) and tris-chelated cations [Cu(bpy)3](2+) occupying the vacancies of the framework. In compound 1 magnetic order is confirmed below 12.

Crystal structures and magnetic properties of a set of dihalo-bridged oxalamidato copper(II) dimers.

A set of four copper(ii) complexes, and (X = Cl, Br; = N-(l-leucine methyl ester)-N'-((2-pyridin-2-yl)methyl)oxalamide and = N-benzyl-N'-((2-pyridin-2-yl)methyl)oxalamide), have been synthesized and characterized by X-ray structural analysis, electron paramagnetic resonance (EPR) spectroscopy on single crystals and by SQUID magnetization measurements. X-ray diffraction studies show one-dimensional hydrogen bonded networks of dimeric copper(ii)-complexes bridged by two halide ions and with the two metal centers 3.44-3.

EPR study of polyaniline synthesized enzymatically in the presence of submicrometer-sized AOT vesicles.

EPR spectroscopy was used to examine the magnetic properties of two enzymatically synthesized polyaniline (PANI) samples obtained in the presence of submicrometer-sized vesicles formed from sodium bis(2-ethylhexyl)sulfosuccinate (AOT) as templates. PANI-HRPC-AOT was synthesized with horseradish peroxidase isoenzyme C (HRPC) and hydrogen peroxide (H2O2) as oxidant while PANI-TvL-AOT was prepared with Trametes versicolor laccase (TvL) and dioxygen (O2) as oxidant. A commercial conductive sample of the emeraldine salt form of polyaniline (PANI-ES) was also used for comparison in order to correlate the experimental data obtained for PANI-HRPC-AOT and PANI-TvL-AOT with the properties of the well-characterized PANI-ES.

The use of Trametes versicolor laccase for the polymerization of aniline in the presence of vesicles as templates.

The enzymatic polymerization of aniline to polyaniline (PANI) with Trametes versicolor laccase (TvL) as catalyst and dioxygen (O₂) as oxidant was investigated in an aqueous medium containing unilamellar vesicles with an average diameter of about 80 nm formed from AOT (=sodium bis(2-ethylhexyl) sulfosuccinate). Compared to the same reaction carried out with horseradish peroxidase isoenzyme C (HRPC) as catalyst and hydrogen peroxide (H₂O₂) as oxidant, notable differences were found in the kinetics of the reaction, as well as in the characteristics of the PANI obtained. Under comparable optimal conditions, which are pH 3.

The effect of thermal treatment of radiation-induced EPR signals of different polymorphic forms of trehalose.

Electron paramagnetic resonance (EPR) signals induced by γ-radiation in different polymorphic forms of trehalose were studied with dosimetry applications in view. Dose response of trehalose in terms of the concentration of induced paramagnetic centers was studied in the dose range from 0.5 to 50 kGy.

Effect of glassy modes on electron spin-lattice relaxation in solid ethanol.

Electron spin-lattice relaxation (SLR) of TEMPO radical was measured in the crystalline and glassy states of deuterated ethanol in the temperature range 5-80K using X-band electron paramagnetic resonance (EPR). The measured SLR rates are higher in the glassy than in crystalline state and the excess SLR rate in glassy state is much lower than in ethanol. This result suggests that extra modes in glassy state, i.

Investigation of the nitrogen hyperfine coupling of the second stable radical in γ-irradiated l-alanine crystals by 2D-HYSCORE spectroscopy.

The second stable radical, NH(3)(+)C()(CH(3))COO(-), R2, in the γ-irradiated single crystal of l-alanine and its fully (15)N-enriched analogue were studied by an advanced pulsed EPR technique, 2D-HYSCORE (two-dimensional hyperfine sublevel correlation) spectroscopy at 200K. The nitrogen hyperfine coupling tensor of the R2 radical was determined from the HYSCORE data and provides new experimental data for improved characterization of the R2 radical in the crystal lattice. The results obtained complement the experimental proton data available for the R2 radical and could lead to increased accuracy and reliability of EPR spectrum simulations.

A multi-frequency EPR spectroscopy approach in the detection of boson peak excitations.

The influence of boson peak (BP) excitations on low-temperature spin-lattice relaxation rate of a paramagnetic center embedded in a glassy matrix is investigated in the context of multi-frequency electron paramagnetic resonance (EPR) detection. In the theoretical analysis, the transition rate of spin one-half in the presence of a phonon field is calculated within the approximation of Fermi's golden rule. Several phonon densities of states are compared, among which one originating from a model of quasi-localized vibrations has been introduced into electron spin relaxation formalism for the first time.

Fast motion in molecular solids at low temperatures: evidence from a pulsed electron paramagnetic resonance study of nitroxyl radical relaxation.

We have investigated the electron phase-memory relaxation time of the nitroxyl radical 2,2,6,6-tetramethylpiperidine-1-oxyl at temperatures between 5 and 80 K in crystalline and glassy states of ethanol using pulsed X-band electron paramagnetic resonance spectroscopy. The results indicate that the transition from the slow to fast motion regimes of the paramagnetic center occurs upon further cooling of the sample below ∼20 K. We provide experimental evidence that this phenomenon cannot be ascribed to the impact of hyperfine interactions with methyl protons in the system, but it can be instead a signature of the coupling of the electron spin with the boson peak excitations of the lattice.

Single crystals of DPPH grown from diethyl ether and carbon disulfide solutions - crystal structures, IR, EPR and magnetization studies.

Single crystals of the free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) obtained from diethyl ether (ether) and carbon disulfide (CS₂) were characterized by the X-ray diffraction, IR, EPR and SQUID magnetization techniques. The X-ray structural analysis and IR spectra showed that the DPPH form crystallized from ether (DPPH1) is solvent free, whereas that one obtained from CS₂ (DPPH2) is a solvate of the composition 4DPPH·CS₂. Principal values of the g-tensor were estimated by the X-band EPR spectroscopy at room and low (10 K) temperatures.

ENDOR study on the dynamic properties of the first stable paramagnetic center in gamma-irradiated L-alanine crystals.

Dynamic properties of the first stable l-alanine radical, SAR1, induced by gamma-irradiation of l-alanine crystals, have been investigated by the electron nuclear double resonance technique (ENDOR). The study focuses on the dynamic properties of the alpha-proton hyperfine splitting in the temperature range from 180 to 320 K. In this region the motion of the NH(3)(+) and CH(3) groups exhibits slow and fast motional dynamics in comparison to the nuclear and electron Larmor frequencies, respectively.

Symmetry-breaking defect in coupled dipole-proton system of hydrogen-bonded ferroelectric.

We consider the coupled dipole-proton system of hydrogen-bonded ferroelectric crystal with one defect dipole that is coupled more strongly with the protons than the original dipole. This defect dipole simulates the symmetry-breaking defects that are often introduced in the crystals as probes in the electron paramagnetic resonance (EPR) experiments. A particular attention is paid to the explanation of strong isotope effects that have been detected in the measurements of static and dynamic properties of the pure crystals and the symmetry-breaking defects.

Evidence for disorder in L-alanine lattice detected by Pulsed-EPR spectroscopy at cryogenic temperatures.

The unusual behavior of lattice dynamics of L-alanine has been assigned to intermolecular dynamics and localization of vibrational energy. Recent heat capacity and Pulsed-EPR measurements support presence of thermally activated dynamic orientational disorder in the L-alanine lattice below 20 K. In the present study, the additional evidence for possible thermally activated disordered behavior of L-alanine lattice have been obtained by investigating dependences of longitudinal relaxation time of first stable L-alanine radical, SAR1, on sample cooling rates for the same low temperature interval.

Thermal stability of radiation-induced free radicals in gamma-irradiated L-alanine single crystals.

Decay of the radiation-induced stable free radicals in l-alanine single crystals and powders at the temperatures from 379 to 476 K was examined by electron paramagnetic resonance. For single crystals, the calculated activation energy of the radical decay is 104.3+/-1.

Heat capacity and electron spin echo evidence for low frequency vibrational modes and lattice disorder in L-alanine at cryogenic temperatures.

With the view of understanding the low frequency (40-50 cm(-1)) motional processes in L-alanine around 4 K, we have carried out heat capacity (CP) and electron spin echo (ESE) measurements on L-alanine and L-alanine-d7. The obtained CP data show the so-called boson peak (seen as a maximum in CP/T3 versus T plots) in the low temperature region (1.8-20 K).

An EPR method for probing surface magnetic fields, dipolar distances, and magnetization fluctuations in single molecule magnets.

We outline a spectroscopic method for probing the effective magnetic field B on the surface of crystals of the single molecule magnet (SMM) [(C6H15N3)6Fe8(mu3-O)2(mu2-OH)12]Br7(H2O)Br.H2O, (Fe8Br8). This technique utilizes the line shape changes in the EPR spectra of the organic radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) (g = 2.

Probing magnetic fields on crystals of the nanomagnet Mn12-acetate by electron paramagnetic resonance.

We report on electron paramagnetic resonance (EPR) probing of magnetic fields and magnetic field gradients near the surface of a single crystal of the nanomagnet [Mn12O12(CH3COO)16(H2O)4].2CH3COOH.4H2O (Mn12-Ac).

Observation of symmetry lowering and electron localization in the doublet-states of a spin-frustrated equilateral triangular lattice: Cu3(O2C16H23) x 1.2C6H12.

Cu3(O2C16H23)6.1.2C6H12, containing a Cu36+ core in an equilateral triangle geometry, has been found to be a versatile model system for investigating the spin-frustration phenomenon in a triangular lattice.

A pulse EPR study of longitudinal relaxation of the stable radical in gamma-irradiated L-alanine.

The longitudinal relaxation rate of the first stable alanine radical, SAR1, was studied by employing pulse EPR technique over a wide temperature interval (5-290 K). The complex nonexponential recovery of the longitudinal magnetization in this temperature interval has been described with two characteristic relaxation times, 1/T*(1a) as the faster component and 1/T*(1b) as the slower component, respectively. It was shown that 1/T*(1a) is strongly affected by the CH(3) group dynamics of the SAR1 center.