X-band Electron Spin Relaxation Times for Four Aromatic Radicals in Fluid Solution and Comparison with Other Organic Radicals

X-band electron spin relaxation times of BDPA (1:1 α,γ-bisdiphenylene-β-phenylallyl), galvinoxyl 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy, DPPH (2,2-diphenyl-1-picrylhydrazyl) and thianthrene radicals in fluid solution were measured by electron spin echo and inversion recovery at ambient temperature. Tumbling correlation times are estimated to be in the range of 20–30 ps. In this fast tumbling regime T ₁ ~ T ₂. Relaxation times are compared with previously reported values for symmetrically substituted triarylmethyl, semiquinone, and nitroxide radicals. The concentration dependence of spin lattice relaxation for neutral BDPA in toluene is about 10³ times greater than for anionic trityl radicals in water. T ₁ decreases in the order carbon-center BDPA > galvinoxyl > DPPH > thianthrene. The dominant relaxation mechanisms are proposed to be a local mode for BDPA, spin rotation, local mode and modulation of anisotropic proton hyperfine coupling for galvinoxyl, modulation of anisotropic nitrogen hyperfine for DPPH, and spin rotation plus modulation of anisotropic proton hyperfine coupling for thianthrene.     

Features of spin exchange in nitroxide biradicals in the ionic liquid bmimPF<Subscript>6</Subscript>

The intramolecular electron spin exchange has been studied by electron paramagnetic resonance (EPR) spectroscopy in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) for various nitroxide biradicals as a function of temperature and the nature of the connecting bridge between two >NO^· centers. Temperature variations of the isotropic nitrogen hyperfine splitting constant a and exchange integral values |J/a| were measured from EPR spectra and analyzed. Thermodynamic parameters of the conformational rearrangements were obtained. The spin exchange in rigid and flexible biradicals dissolved in the ionic liquid bmimPF₆ was compared with that in toluene solutions. Interesting features of the spin exchange in biradicals in ionic liquid were observed and explained as a result of the specific intramolecular conformational transitions. The first example of a rather rigid biradical molecule becoming flexible under the influence of an ionic liquid is reported.     

Pulse field-sweep EPR of copper proteins

Pulse field-sweep EPR (PFSEPR) is developed as a low-power, microwave pulse technique to resolve hyperfine structure underlying inhomogeneously broadened EPR lines. PFSEPR arises from transfer of saturation due to spin state mixing from forbidden Δm_I ≠ 0 EPR transitions. We report its first use to resolve large copper hyperfine couplings which are unresolved by standard X-band EPR. As applied to copper, PFSEPR has better sensitivity than ENDOR with comparable spectral resolution. The details of energy levels and state mixing which account for PFSEPR transitions in these copper systems are developed here. PFSEPR transitions from stellacyanin provide hyperfine and quadrupole couplings in good agreement with those predicted by various EPR simulations and determined by ENDOR. Copper couplings from the Cu_A signal of cytochrome-c oxidase are comparable to previously published estimates, but PFSEPR suggests underlying state mixing of copper levels.     

An electron paramagnetic resonance and density-functional theory study on the methyl isotropic hyperfine coupling constants in gamma-irradiated 2,6-di-tert-butyl-4-methylphenol

Single crystal of gammairradiated 2,6-di-tert-butyl-4-methylphenol (BHT) was investigated using an electron paramagnetic resonance (EPR) technique at different orientations in the magnetic field at room temperatures. Taking into consideration the chemical structure and the experimental spectra of the irradiated single crystal of BHT, we assumed that one phenoxyltype paramagnetic species was produced having an unpaired electron localized at the methyl fragment side of the phenyl ring. Depending on this assumption, one possible radical was modeled using the B3LYP/6-311+G(d) level of density-functional theory. EPR parameters were calculated for these modeled radical using the B3LYP/TZVP and B3LYP/EPR-III level. The averaged value of isotropic hydrogen hyperfine coupling constants of rotating methyl functional group of phenoxyl radical is calculated for the first time. Theoretically calculated values of the modeled radical are in reasonably good agreement with the experimental data determined from the spectra (differences in averaged coupling constant values smaller than 5%, and differences in isotropic g values fall into 1 ppt).     

Effect of the amplitude of excitation pulses on the shape of photon-echo signals in two-level systems

It is theoretically established that multiple photon-echo signals reflect the oscillatory structure of the primary echo signal, which arises under the conditions of collinear excitation of two-level active centers by laser pulses having the same width but different amplitudes. It is shown that the oscillatory structure of the primary photon echo exists within the intervals (?t ₁, t ₁) and (?2t ₁, 2t ₁), where t ₁ is the pulse width. It is found that, when the pulse width is of the same order of magnitude as the delay between the pulses and the amplitudes of the excitation pulses obey certain relations, the oscillatory structure of the primary photon-echo signal becomes asymmetric. In the mode of quadratic detection of the primary photon-echo signal, the asymmetric oscillatory structure of the primary echo manifests itself as a manifold of isolated signals (multiple photon echoes), with the time intervals between these signals being equal to the pulse width.     

Solid-state photochemical generation of stable radical pairs from bis(aryloxy)phosphine azide precursors

Two types of radical pairs, stable at room temperature, were found in monocrystals of 2,6-di-tert-butyl-4-methylphenol doped with bis(2,6-di-tert-butyl-4-methoxyphenoxy) phosphine azide after photoirradiation using a Xe arc lamp. One pair consists of two 2,6-di-tert-butyl-4-methoxyphenoxyls (RP₁), the other of 2,6-di-tert-butyl-4-methoxyphenoxyl and 2,6-di-tert-butyl-4-methylphenoxyl (RP₂), as indicated by their EPR hyperfine splitting. In the temperature range of 120–200 K RP₁ accumulates 7 times faster than at 77 K. Explanations for this photoaccumulation as well as a mechanism of RP formation are proposed.     

EPR and optical spectroscopy of impurities in two synthetic beryls

Two synthetic beryls (Al₂Be₃Si₆O₁₈) of different color (purple and blue-green) were studied with electron paramagnetic resonance (EPR) and optical spectroscopy. In both crystals, the known spectra of Cu²⁺ and Fe³⁺ were observed with the same relative intensity. In the purple sample heated at 700°C in hydrogen atmosphere, two different kinds of Mn²⁺ EPR spectra were observed. The main one is pseudoaxial, it arises from ions substituted for Al³⁺ at position 4c of the structure. The weaker one is more complex, it has orthorhombic symmetry and is characterized by an unusually large zero-field splitting (B ₂⁰ = 741 · 10⁻⁴ cm⁻¹) and an isotropic hyperfine constantA = 70 G. This spectrum arises from Mn²⁺ at position 6f in the structure, normally occupied by Be. From optics, the blue-green color arises from Cu²⁺, while the purple one is due to Mn³⁺.     

Relaxation and quantum beat of picosecond backward echo in Na vapor

The backward photon echo has been realized for the first time in the picosecond regime on the Na D line, and used to measure collisional relaxation of the Na-Ar system. The separations of the successive 10 ps excitation pulses were varied from 300 to 1500 ps. By means of a streak camera, we directly observed a quantum beat of the echo pulse arising from the hyperfine splitting of the 3S_{$\text{1}\text{2}$} ground state of Na.     

Relaxation times and line widths of isotopically-substituted nitroxides in aqueous solution at X-band

Optimization of nitroxides as probes for EPR imaging requires detailed understanding of spectral properties. Spin lattice relaxation times, spin packet line widths, nuclear hyperfine splitting, and overall lineshapes were characterized for six low molecular weight nitroxides in dilute deoxygenated aqueous solution at X-band. The nitroxides included 6-member, unsaturated 5-member, or saturated 5-member rings, most of which were isotopically labeled. The spectra are near the fast tumbling limit with T₁∼T₂ in the range of 0.50–1.1 μs at ambient temperature. Both spin–lattice relaxation T₁ and spin–spin relaxation T₂ are longer for ¹⁵N- than for ¹⁴N-nitroxides. The dominant contributions to T₁ are modulation of nitrogen hyperfine anisotropy and spin rotation. Dependence of T₁ on nitrogen nuclear spin state m_I was observed for both ¹⁴N and ¹⁵N. Unresolved hydrogen/deuterium hyperfine couplings dominate overall line widths. Lineshapes were simulated by including all nuclear hyperfine couplings and spin packet line widths that agreed with values obtained by electron spin echo. Line widths and relaxation times are predicted to be about the same at 250 MHz as at X-band.     

Features of Spin Exchange in Short-Chain Nitroxide Biradicals in Ionic Liquids

The intramolecular electron spin exchange has been studied by electron paramagnetic resonance (EPR) spectroscopy in the room temperature ionic liquids (RTIL) 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) and 1-octyl-3-methylimidazolium tetrafluoroborate (omimBF₄) for three nitroxide biradicals with analogous structures of the connecting bridge between two >N–O· centers as a function of temperature. Temperature variations of the isotropic nitrogen hyperfine splitting constant a, and exchange integral values |J/a| were determined from EPR spectra and analyzed. Thermodynamic parameters of the conformational rearrangements were obtained. The spin exchange in rather rigid short-chain biradicals dissolved in omimBF₄ and bmimPF₆ was compared with that in toluene solutions. Interesting features of the spin exchange in biradicals in RTIL were observed and explained as a result of the specific intramolecular conformational transitions. Examples when rather rigid biradical molecules become flexible under an influence of RTIL are reported.     

New electron centers in neutron-irradiated natural quartz

EPR measurements on neutron-irradiated natural quartz crystals from Brazil revealed the presence of two new electron centers, each with hyperfine structure due to one proton. In one of these centers this hyperfine splitting is typical for H^? which most likely substitutes for an oxygen whereas in the other a much smaller splitting due to an OH group was observed. The properties of these centers are compared with those of the E^′_n centers with closely related structures.     

Separation of the ortho and para NMR signals in solid deuterium via DQ filtering

Double quantum (DQ) filtering is shown to lead to an effective separation of the NMR signals from the para (I = 1) and ortho (I = 2) molecules in solid deuterium. The separation is achieved by the pulse sequence 90_φ^°–t_pr–90_φ^°–t_ev–90_x^°–t, where the phase-cycled first two pulses create the DQ coherence. Two components are observed after the third pulse; the para signal shows the maximum at a short time t while the ortho signal reaches the maximum at a longer t. The observed signal can be expressed as ∑_I [F_I(t_pr − t) − F_I(t_pr + t)], where F_I(t) is a proper fitting function for the free induction signal of the para and ortho molecules (with I = 1 or 2, respectively). Numerical fits to experimental data at 4.2 and 2 K show that this method can be used to determine the ratio F₁(0)/F₂(0) and thus, because the initial value F_I(0) is proportional to the respective magnetization before the pulse sequence, the ortho and para concentrations in solid deuterium.     

Ionization energies and Koopmans' theorem

Trends in the hyperfine splitting constants of alkylated 1,4-semiquinones can be explained by a consideration of inductive and steric influences of the substituent groups, in conjunction with effects of the solvating medium. Using this model, the splittings for t-butyl semiquinones are rationalized and the additivity principle is given a theoretical foundation.     

Pulsed ENDOR Spectroscopy at Large Thermal Spin Polarizations and the Absolute Sign of the Hyperfine Interaction

It is shown that in pulsed Mims-type ENDOR experiments performed at 95 GHz and 1.2 K the sign of the ENDOR signal can be positive, corresponding to an increase of the stimulated echo intensity, as well as negative, corresponding to a decrease of the stimulated echo. The positive “anomalous” sign is not observed at conventional EPR frequencies. It is explained that the effect arises through spin–lattice relaxation in the situation of large thermal spin polarizations and that it allows the determination of the absolute sign of the hyperfine interaction.     

E-H-Zyklotronechos in Plasmen

A new echo type with free electrons in a slight inhomogeneous magnetic field excited by one electric and one magnetic pulse is calculated. Thus features of cyclotron echos and spin echoes are combined. The first electric pulse accelerates all (cold) particles to the same velocity as in the case of usual cyclotron echoes. The second magnetic pulse (at t = τ) rotates the plane of precession in phase space, quite in analogy to the motion of magnetic moments in the case of spin echoes. The echo arises at t = 2τ. The E-H echoes make relaxation and diffusion measurements in plasmas possible, using the methods proved useful in spin echo technique. There are no complications as in the case of E-E cyclotron echoes which are based on the fact that a velocity-dependent collision frequency is necessary for the nonlinearity of that echo mechanism.     

Characteristics of ESEEM and HYSCORE spectra of S>1/2 centers in orientationally disordered systems

One- and two-dimensional electron-spin echo envelope modulation (ESEEM) spectra of Kramers’ multiplets in orientationally disordered systems are simulated using a simple mathematical model. A fairly general high-field spin Hamiltonian is considered with a general g-tensor and arbitrary relative orientations between all tensors involving the electron-spin S, the nuclear spin I, and their interaction. The zero field splitting (ZFS) and the nuclear quadrupole interactions are, however, approximated by their respective secular part in a way that retains all orientation dependencies and it is assumed that the nuclear quadrupole interaction is smaller than the hyperfine interaction. These approximations yield an effective sublevel nuclear Hamiltonian for each EPR transition and are sufficient to account for the most important characteristics of the ESEEM spectra of high electronic multiplets in orientationally disordered systems. Moreover, they allow to obtain some analytical expressions that for I=1/2 illuminate important aspects of 2D hyperfine sublevel correlation (HYSCORE) experiments in S=3/2, 5/2 systems. The pulses are considered as ideal and selective with respect to the different EPR transitions. The contributions of the latter to the echo intensity are weighed according to their different nutation angles and equilibrium Boltzmann populations. For simple axial cases with I=1/2, analytical expressions, analogous to the S=1/2 case, were derived for: (i) the modulation depth, (ii) the lineshapes of the HYSCORE cross-correlation ridges, and (iii) ENDOR powder pattern. Experimental results obtained from Mn(D₂O)₆²⁺ and VO(D₂O)₅²⁺ in frozen solutions are presented, compared, and analyzed in light of the theoretical part.     

Quantitative Evaluation of the Lactate Signal Loss and Its Spatial Dependence in PRESS Localized H NMR Spectroscopy

Localized ¹H NMR spectroscopy using the 90°−t₁−180°−t₁+t₂−180°−t₂−Acq. PRESS sequence can lead to a signal loss for the lactate doublet compared with signals from uncoupled nuclei which is dependent on the choice of t₁ and t₂. The most striking signal loss of up to 78% of the total signal occurs with the symmetrical PRESS sequence (t₁=t₂) at an echo time of 2/J (290 ms). Calculations have shown that this signal loss is related to the pulse angle distributions produced by the two refocusing pulses which leads to the creation of single quantum polarization transfer (PT) as well as to not directly observable states (NDOS) of the lactate AX₃ spin system: zero- and multiple-quantum coherences, and longitudinal spin orders. In addition, the chemical shift dependent voxel displacement (VOD) leads to further signal loss. By calculating the density operator for various of the echo times TE=n/J, n=1, 2, 3, …, we calculated quantitatively the contributions of these effects to the signal loss as well as their spatial distribution. A maximum signal loss of 75% can be expected from theory for the symmetrical PRESS sequence and TE=2/J for Hamming filtered sinc pulses, whereby 47% are due to the creation of NDOS and up to 28% arise from PT. Taking also the VOD effect into account (2 mT/m slice selection gradients, 20-mm slices) leads to 54% signal loss from NDOS and up to 24% from PT, leading to a maximum signal loss of 78%. Using RE-BURP pulses with their more rectangular pulse angle distributions reduces the maximum signal loss to 44%. Experiments at 1.5 T using a lactate solution demonstrated a maximum lactate signal loss for sinc pulses of 82% (52% NDOS, 30% PT) at TE=290 ms using the symmetrical PRESS sequence. The great signal loss and its spatial distribution is of importance for investigations using a symmetrical PRESS sequence at TE=2/J.     

Nutation electron spin echo ofE-centers in quartz

Attenuation of the signals of the nutation echo of E’-centers in crystalline and glass quartz was experimentally investigated at room temperature. The nutation echo in EPR was excited in the single-photon regime and formed by two Zeeman-field pulses with duration t₁ and t₂ (t₁<t₂) and time interval between them τ. The echo signal was recorded during the second pulse at t≈2t₁+τ. It was established that this signal attenuation, measured as t₁ increased, follows an, exponential law, its rate Γ is much less than 1/T₂ (T₂ is the transverse relaxation time), and it linearly increases with an increase in the amplitude of the exciting SHF field B₁. The parameters of the dependence of Γ on B₁ correlate with the parameters of the analogous dependence revealed previously for attenuation of nutation of E’-centers in quartz in the two-photon regime at T=4.2 K. At the same time, the value of Γ measured with different values of τ is independent of B₁ and is equal to 1/T₁, where T₁ is the longitudinal relaxation time. A. N. Sevchenko Scientific Research Institute of Applied Physical Problems, 7, Kurchatov St., Minsk, 220064, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 405–411, May–June, 1998.     

Evidence for the development of persistent carbon-centered radicals from a benzyl phenolic antioxidant: an electron paramagnetic resonance study

Radicals have been generated from the benzyl phenolic antioxidant 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) benzene, carrying out oxidative and hydrogen abstraction reactions. Transient phenoxyl radicals were directly visualized but only persistent carbon-centered radicals were monitored by electron paramagnetic resonance (EPR). The experimental EPR results let us rationalize our analysis as the sum of two different radicals. One, called the methylene radical, developed from the loss of a benzylic hydrogen gave place to a doublet of triplets witha _CH^H≅2.7 mT anda _PH^H=0.165 mT. Besides, the methyl radical, developed after an intramolecular hydrogen transfer involving a methyl group on the central aromatic ring of the molecule, formed a triplet of triplets, witha ₁^H around 0.060 mT anda ₂^H=0.169 mT. All the contact interactions were tested by EPR simulation of the experimental data.