EPR investigation of a-Si:H aerosol particles formed under silane thermal decomposition

The dangling bond defects were investigated in a-Si:H particles formed under silane thermal decomposition in flow reactor. EPR together with hydrogen evolution method were used. The experimental results allowed us to conclude that there are two kinds of dangling bond defects in a-Si:H aerosol particles. The defects of the first kind are localized on the surface of interconnected microvoids and microchannels (surface dangling bonds) and those of the second kind are embedded in amorphous silicon network (volume dangling bonds). The thermal equilibration of dangling bonds and temperature dependence of equilibrium dangling bond concentration were investigated. It was found that at temperatures > 400 K the dangling bond concentrationNApplied Magnetic Resonance _s reversibly depends on sample temperature. The volume dangling bond concentration increases with temperature increasing (the effective activation energy of dangling bond formationU > 0), and the surface dangling bond concentration decreases with temperature increasing (U < 0). It has been found that EPR line is considerably asymmetric for samples with high hydrogen content and for low hydrogen content the EPR line is weakly asymmetric. A conclusion was drawn that the asymmetry degree depends on amorphous silicon lattice distortions. This conclusion has been confirmed by EPR spectra simulations.     

CIDNP in photolysis of acetone solutions in plastic crystals of cyclohexane-d12

The emissive CIDNP was observed during photolysis of acetone solutions in solid cyclohexane-d₁₂. The polarization is assumed to arise in contact triplet radical pairs as a result of their T_-S, conversion and their recombination.     

Pulsed electron double resonance (PELDOR) and its applications in free-radicals research

The papers related to the theoretical background and experimental investigations by pulsed electron double resonance (PELDOR) are reviewed. The main aim of this pulsed ESR application is to study the dipole-dipole spin interaction. In PELDOR the ESR spectrum is excited by two ESE pulses at frequencyω _a and additional pumping pulse atω _b. Decay functionV(T) of the ESE signal, when the time intervalT between the first ESE pulse and pumping pulse is varied, contains the information on dipole-dipole couplings in the spin system. The kinetics ofV(T) decay strongly depends upon distance, mutual orientation inside interacting spin pairs and space distribution of radicals throughout the sample. The distances between spins which were measured or estimated using PELDOR in the papers reviewed are in the range of 15 ÷ 130 Å. This pulsed ESR technique turns now to be a powerful supplement to conventional ESE in studying the free radicals space distribution..     

Two-dimensional hyperfine sublevel correlation spectroscopy: powder features for S=1/2, I=1

The lineshapes of two-dimensional magnetic resonance spectra of disordered or partially ordered solids are dominated by ridges of singularities in the frequency plane. The positions of these ridges are described by a branch of mathematics known as catastrophe theory concerning the mapping of one 2D surface onto another. We systematically consider the characteristics of HYSCORE spectra for paramagnetic centers having electron spin S=1/2 and nuclear spin I=1 in terms of singularities using an exact solution of the nuclear spin Hamiltonian. The lineshape characteristics are considered for several general cases: zero nuclear quadrupole coupling; isotropic hyperfine but arbitrary nuclear quadrupole couplings; coincident principal axes for the nuclear hyperfine and quadrupole tensors; and the general case of arbitrary nuclear quadrupole and hyperfine tensors. The patterns of singularities in the HYSCORE spectra are described for each case.     

Conformational Properties of the Spin-Labeled Tylopeptin B and Heptaibin Peptaibiotics Based on PELDOR Spectroscopy Data

X-Band pulsed electron–electron double resonance (PELDOR) spectroscopy was used to investigate for the first time the magnetic dipole–dipole interaction between spin labels for frozen glassy methanol solutions at 77 K of double spin-labeled, medium-length peptaibiotics, namely, tylopeptin B and heptaibin. This study was conducted on tylopeptin labeled at positions 3 and 13 (T313) and heptaibin labeled at positions 2 and 14 (H214). PELDOR data analysis was carried out using the theory developed for short inter-spin distances. The distance distribution functions between spin labels for T313 (maximum at 1.76 nm, half-width of 0.07 nm) and H214 (maximum at 2.30 nm, half-width of 0.065 nm) were determined. It is found that the distance distribution function for peptide T313 has the Gaussian shape. The main part of the distance spectrum for H214 has Gaussian shape and additional less intensive broad lines are shifted to high distances range 2.5–3.5 nm. The upper limit of distance spectrum in this case corresponds approximately to the length of extended peptide molecule and the number of such configurations is low. Intramolecular distances between the labels at maxima observed allowed us to assign α-helical conformation to T313 and 3₁₀-helical structure to H214 in methanol solution.     

C(sp2)‐Coupled Nitronyl Nitroxide and Iminonitroxide Diradicals

Spin‐labelled compounds are widely used in chemistry, physics, biology and the materials sciences but the synthesis of stable high‐spin organic molecules is still a challenge. We succeeded in synthesising heteroatom analogues of the 1,1,2,3,3‐pentamethylenepropane (PMP) diradicals with two nitronyl nitroxide ( DR¹ ) and with two iminonitroxide ( DR² ) fragments linked through the C(sp²) atom of the nitrone group. According to magnetic susceptibility measurements, EPR data and ab initio calculations at the (8,6)CASSCF and (8,6)NEVPT2 levels, DR¹ and DR² have singlet ground states. The singlet–triplet energy splitting (2J) is low (J/k=?7.4 for DR¹ and ?6.0 K for DR² ), which comes from the disjoint nature of these diradicals. The reaction of [Cu(hfac)₂] with DR¹ gives rise to different heterospin complexes in which the diradical acts as a rigid ligand, retaining its initial conformation. For the [{Cu(hfac)₂}₂( DR¹ )(H₂O)] complex, sufficiently strong ferromagnetic interactions (J₁/k=42.7 and J₂/k=14.1 K) between two coordinating Cu^II ions and DR¹ were revealed. In [{Cu(hfac)₂}₂( DR¹ )(H₂O)][Cu(hfac)₂(H₂O)], the very strong and antiferromagnetic (J/k=?416.1 K) exchange interaction between one of the coordinating Cu^II ions and DR¹ is caused by the very short equatorial Cu?O bond length (1.962 Å).     

Dipole-dipole interactions of high-spin paramagnetic centers in disordered systems

Dipole-dipole interactions between distant paramagnetic centers (PCs) where at least one PC has spinS>1/2 are examined. The results provide a basis for the application of pulsed electron-electron double resonance method to the measurement of distances between PCs involving high-spin species. A projection operator technique based on spectral decomposition of the secular Hamiltonian is used to calculate electron paramagnetic resonance (EPR) line splitting caused by the dipole coupling. This allows calculation of operators projecting an arbitrary wave function onto high-spin PC eigenstates when the eigenvectors of the Hamiltonian are not known. The effective spin vectors — that is, the expectation values for vector spin operators in the PC eigenstates — are calculated. The dependence of these effective spin vectors on the external magnetic field is calculated. There is a qualitative difference between pairs having at least one integer spin (non-Kramers PC) and pairs of two half-integer (Kramers PC) spins. With the help of these effective spin vectors, the dipolar line shape of EPR lines is calculated. Analytical relations are obtained for PCs with spinS=1/2 and 1. The dependence of Pake patterns on variations of zero-field splitting, Zeeman energy, temperature and dipolar coupling are illustrated.     

Dynamic nuclear polarization in electron spin echo

It is shown that under the action of a proper microwave pulse sequence the equilibrium polarization of the electron spin may be transferred dynamically to the longitudinal nuclear magnetization which will oscillate due to the nuclear spin precession around the effective fields relating to differnt electron quantum number manifolds. These oscillations may be measured directly in the radiofrequency band. Analytical formulae are obtained for the case when all the nuclei coupled to an unpaired electron have spins of 1/2.