Electron paramagnetic resonance and electron nuclear double resonance of the AsO4 4- centre in X-irradiated KH2AsO4

Electron paramagnetic resonance studies of the AsO₄ ^4- centre in X-irradiated crystals of KH₂AsO₄ in the ferroelectric phase at 77 and 4·2 K are reported. The symmetry of the spin-hamiltonian has been found to be orthorhombic, and the g tensor and the A tensor describing the interaction of the unpaired electron with the arsenic nucleus (I = 3/2) have been obtained. Domain splitting has been observed in he spectra recorded in the ab plane of the crystal. By studying these spectra in the presence of an applied electric field, it has been possible to plot the hysteresis curve of ferroelectric KH₂AsO₄. Electron-nuclear double resonance (ENDOR) of protons surrounding the AsO₄ ^4- units has been studied at 4·2 K. Two sets of ENDOR lines have been found arising from the protons in the two equilibrium positions (labelled ‘ close ’ and ‘ far ’) along the hydrogen bonds linking the AsO₄ tetrahedra. The angular variation of the ENDOR lines from both ‘ close ’ and ‘ far ’ protons has been plotted in the crystal symmetry planes. The observed ENDOR frequencies have been fitted to those calculated from the numerical diagonalization of the Hamiltonian. The superhyperfine parameters for the ‘ close ’ and ‘ far ’ protons thus obtained are found to be quite anisotropic. The ENDOR results are shown to explain all details of the partially-resolved proton superhyperfine structure at room temperature as well as at low temperatures. An isotropic contact hyperfine coupling of -2·875 MHz of the unpaired electron to the proton in the ‘ far ’ position of the hydrogen bond has been determined, providing direct evidence for covalency in the hydrogen bonding in KH₂AsO₄ crystals.     

Electron nuclear quadruple resonance for assignment of overlapping spectra

Multiple resonance methods are important tools in EPR for revealing the network of hyperfine levels of free radicals and paramagnetic centers. The variations of electron nuclear double resonance (ENDOR) or electron spin-echo envelope modulation (ESEEM) techniques help to correlate nuclear frequencies with each other. These methods have limited utility when there is extensive overlap or suspected overlap in the EPR spectrum between different species or different orientations. In the ENDOR spectrum, overlap and second-order shifts of lines also leads to ambiguity in assignment and interpretation. A new electron nuclear multiple resonance method is presented here that is based on population transfer ENDOR. It is a quadruple resonance method that correlates ENDOR lines and reveals the network of hyperfine levels in samples with unoriented paramagnetic species and in samples with overlapping EPR or ENDOR lines.     

Local structure of bivalent copper centers in SrF2 crystals: An ENDOR spectroscopic study

Structural distortions of the SrF₂ crystal lattice near the bivalent copper impurity Jahn-Teller center are investigated by the ENDOR method (v=9.3 GHz, T=4.2 K). The approximate directions and the magnitudes of displacements of a Cu²⁺ impurity ion and its surrounding F^? ions are determined with respect to one of the anionic networks in the crystal matrix. The tensor components for the ligand hyperfine interaction (LHFI) with fluorine ions separated from the impurity by a distance R≤6.2 Å are obtained from the angular dependences of the location of the ENDOR resonance lines. It is found that the parameters of magnetic interactions between the impurity and these ligands contain the contributions determined by the covalence of bonds in the impurity complex and the polarization of electron shells of the ligands.     

EPR and ENDOR Study of a series of free base porphycenes in the photoexcited triplet state

Porphycene is a structural isomer of porphyrin. The photoexcited triplet states of porphycene, 2,7,12,17-tetra-n-propylporphycene and 9,10,19,20-tetra-n-propylporphycene in disordered solid solution were studied by EPR and ENDOR. The ENDOR spectra yield the hyperfine tensor elementsA _zz for each of the different groups of equivalent protons. The dipolar contribution toA _zz is estimated and spin densities are derived from the isotropic contribution. They are compared with results of all-valence-electrons self-consistent field molecular orbital calculations (RHF-INDO/SP and RHF-INDO/S).     

Optically detected E.P.R. and low-field ENDOR of triplet benzophenone

The ENDOR spectrum of ¹³C substituted (carbonyl carbon) triplet excited benzophenone was studied at ca. 100 G applied magnetic field by means of optical detection. The benzophenone was substitutionally dissolved in dibromodiphenylether (DDE). The ENDOR transitions and the E.P.R. transitions were studied as a function of applied field direction in the ab and bc crystal planes. The angle ? between the line joining the phenyl group centres and a principal axis of the fine structure tensor was found to be 23·6° ± 0·02° (standard deviation limited to one set of measurements). The principal axes of the ¹³C hyperfine tensor were within experimental error (±10°) coincident with the fine structure axes. The principal values of the hyperfine tensor were found to be : |A_xx /h| = 43·16 ± 1·84, |A_yy /th| = 22·66 ± 2·50, |A_zz /h| = 10·25 ± 1·30 MHz. The low-field ENDOR does not provide an indication of the signs of these tensor elements, so the value of the isotropic coupling constant cannot be measured. Two values of the anisotropic (dipole) hyperfine tensor elements were deduced on the assumption that the transitions frequencies are mainly determined by interactions between the nuclear spin and electron density on the carbonyl carbon atom. These values were (i) A _xx / ^d /h = 17·82, A_yy /h = -22·68, A_zz /h = -15·14 MHz and (ii) A_xx /h = 39·73, A_yy /h = -26·09, A_zz /h = -13·63 MHz. Set (ii) is consistent with recent calculations of the spin density distribution in triplet benzophenone in which the orbital spin densities are 0·64 for the carbonyl carbon π-orbital, 0·17 for the oxygen π-orbital, and 0·88 for the non-bonding orbital on oxygen (all expressed as fractions of one electron).

Isotope effects on the fine structure constants of triplet benzophenone were measured and found to be consistent with the changes occurring in the spin-orbit coupling with the ground state.

The kinetic parameters for the excitation and de-excitation of the triplet substates were deduced from transient ODMR studies of benzophenone in DDE. The T_z spin state is mainly populated (85–88 per cent) and this is also the most strongly radiative state (k_z ^r = 0·88). The steady-state populations of the three triplet levels are similar.     

Two-dimensional ENDOR-ESEEM correlation spectroscopy

A two-dimensional (2D) experiment that correlates electron-nuclear double resonance (ENDOR) and electron spin-echo envelope modulation (ESEEM) frequencies, useful for unraveling and assigning ENDOR and ESEEM spectra from different paramagnetic centers with overlapping EPR spectra, is presented. The pulse sequence employed is similar to the Davies ENDOR experiment with the exception that the two-pulse echo detection is replaced by a stimulated echo detection in order to enhance the resolution in the ESEEM dimension. The two-dimensional data set is acquired by measuring the ENDOR spectrum as a function of the time interval T between the last two microwave pulses of the stimulated echo detection scheme. This produces a series of ENDOR spectra with amplitudes that are modulated with T. Fourier transformation (FT) with respect to T then generates a 2D spectrum with cross peaks connecting spectral lines of the ESEEM and ENDOR spectra that belong to the same paramagnetic center. Projections along the vertical and horizontal axes give the three-pulse FT-ESEEM and ENDOR spectra, respectively. The feasibility of the experiment was tested by simulating 2D ENDOR-ESEEM correlation spectra of a system consisting of an electron spin (S = (1/2)) coupled to two nuclei (I(1) = I(2) = (1/2)), taking into account experimental conditions such as pulse durations and off-resonance irradiation frequencies. The experiment is demonstrated on a single crystal of Cu(2+) doped l-histidine (Cu-His), containing two symmetrically related Cu(2+) sites that at an arbitrary orientation exhibit overlapping ESEEM and ENDOR spectra. While the ESEEM spectrum is relatively simple and arises primarily from one weakly coupled (14)N, the ENDOR spectrum is very crowded due to contributions from two nonequivalent nitrogens, two chlorides, and a relatively large number of protons. The simple ESEEM projection of the 2D ENDOR-ESEEM correlation spectrum is then used to disentangle the ENDOR spectrum and resolve two sets of lines corresponding to the different sites. Copyright 2000 Academic Press.     

Pulse ENDOR studies on the radical pair P 700 +· A 1 ·− and the photoaccumulated quinone acceptor A 1 ·− of photosystem I

The secondary acceptor A₁ of the electron transport chain(s) of photosystem (PS) I is a phylloquinone (vitamin K₁, VK₁). Pulse electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments at X-band frequencies were performed on the photoaccumulated acceptor radical A ₁ ^·? and the radical pair state P ₇₀₀ ^·+ A ₁ ^·? in PS I ofThermosynechococcus elongatus. The data obtained were compared with data from the respective radical anion of VK₁ in organic solvents. The unusualg tensor magnitude of A ₁ ^·? is explained by the hydrophobic binding pocket of this radical. The hyperfine couplings and the spin (and charge) density distribution is very different for A ₁ ^.? in PS I and VK ₁ ^·? in frozen alcoholic solution. This is attributed to a rather strong one-sided hydrogen bond to A ₁ ^·? . The presence of a hydrogen bond to A ₁ ^·? has only a minor effect ong. The hyperfine coupling constants of A ₁ ^·? determined from the radical pair spectra deviate only slightly from those derived from photoaccumulated A ₁ ^·? in PS I treated with dithionite at high pH. ENDOR resonances of the proton in a H bond were detected and an estimate of the strength and geometry of this bond to A ₁ ^·? was obtained. The significance of the hydrogen bond and other (hydrophobic) interactions of A₁ with the surrounding are briefly discussed.     

Investigation of the Stationary and Transient A 1 ·− Radical in Trp → Phe Mutants of Photosystem I

Photosystem I (PS I) contains two symmetric branches of electron transfer cofactors. In both the A- and B-branches, the phylloquinone in the A₁ site is π-stacked with a tryptophan residue and is H-bonded to the backbone nitrogen of a leucine residue. In this work, we use optical and electron paramagnetic resonance (EPR) spectroscopies to investigate cyanobacterial PS I complexes, where these tryptophan residues are changed to phenylalanine. The time-resolved optical data show that backward electron transfer from the terminal electron acceptors to P₇₀₀^·+ is affected in the A- and B-branch mutants, both at ambient and cryogenic temperatures. These results suggest that the quinones in both branches take part in electron transport at all temperatures. The electron-nuclear double resonance (ENDOR) spectra of the spin-correlated radical pair P₇₀₀^·+A₁^·− and the photoaccumulated radical anion A₁^·−, recorded at cryogenic temperature, allowed the identification of characteristic resonances belonging to protons of the methyl group, some of the ring protons and the proton hydrogen-bonded to phylloquinone in the wild type and both mutants. Significant changes in PS I isolated from the A-branch mutant are detected, while PS I isolated from the B-branch mutant shows the spectral characteristics of wild-type PS I. A possible short-lived B-branch radical pair cannot be detected by EPR due to the available time resolution; therefore, only the A-branch quinone is observed under conditions typically employed for EPR and ENDOR spectroscopies.     

EPR and ENDOR study of an oxygen-vacancy-associated Ti center in RbTiOPO4 crystals

The dominant Ti³⁺ trapped electron center in flux-grown RbTiOPO₄ (RTP) crystals has been characterized using electron paramagnetic resonance (EPR) and electron–nuclear double resonance (ENDOR). This center is produced during an X-ray irradiation at room temperature when a Ti⁴⁺ ion traps an electron and becomes a Ti³⁺ ion, and is best studied in the 30–40 K range. The EPR spectrum contains a three-line hyperfine pattern from two nearly equivalent neighboring ³¹P nuclei, along with hyperfine lines from the ⁴⁷Ti and ⁴⁹Ti nuclei. The g matrix, determined from the angular dependence of the EPR spectrum, has principal values of 1.819, 1.889, and 1.947. Hyperfine matrices for four ³¹P nuclei are obtained from the angular dependence of the ENDOR spectrum. The proposed model for this defect is a Ti³⁺ ion adjacent to an oxygen vacancy at an OT position. Analogies are made to a similar Ti³⁺ center in KTiOPO₄ (KTP) crystals.     

The use of ENDOR to identify the atomic structure of defects in diamond

Although nearly 100 paramagnetic defects have been catalogued in diamond by spin Hamiltonian parameters measured by electron paramagnetic resonance (EPR), very few of these have been unambiguously associated with an atomic model. It has been necessary to use electron nuclear double resonance (ENDOR) to obtain enough information to make proper assignment of such models. The reason for the limitation of EPR, and the way in which ENDOR overcomes these limitations are discussed. The interpretation of hyperfine structure in terms of unpaired electrons in molecular orbitals, and of quadrupole interactions in terms of all electrons, paired and unpaired, as a source of information about molecular structure in diamond, is evaluated by reference to some well documented examples. The measurements so far made by ENDOR on defects in diamond are reviewed, and the salient contribution for the assignment of a model for each defect is explained. The details revealed by ENDOR considerably increase knowledge about defects, particularly those involving substitutional nitrogen atoms. This in turn helps in understanding the complex electron and atom, migration processes which go on under appropriate conditions of temperature and pressure, or optical excitation. The possibilities are discussed for using ENDOR to increase the number of well characterized centres.     

Nuclear relaxation effects in Davies ENDOR variants

A recent article by Yang and Hoffman [T.-C. Yang, B.M. Hoffman, J. Magn. Reson., 181 (2006) 280] presents a ‘Davies/Hahn ENDOR multi-sequence’ in which the α and β peaks of an electron-nuclear double resonance (ENDOR) spectrum can be distinguished. This represents one instance of a family of ENDOR sequences which have no initial microwave inversion pulse, and which can reveal information about nuclear relaxation rates and the signs of hyperfine coupling constants. Here we discuss the more general set of such sequences, which we refer to as Saturated Pulsed ENDOR, and show how signal sensitivity can be optimised within the context of this new technique. Through simulations, we compare its performance to other techniques based on Davies ENDOR, and experimentally illustrate its properties using the non-heme Fe enzyme anthranilate dioxygenase AntDO. Finally, we suggest a protocol for extracting both the magnitude and sign of the hyperfine tensor using a combination of ENDOR techniques.     

The ups and downs of Feher-style ENDOR

A new transient variation of the “Feher-style” electron-nuclear double resonance (ENDOR) method is examined. In this technique, the passage-mode electron paramagnetic resonance (EPR) signal is monitored following the application of a pulsed radio frequency (RF). Continuous-wave and transient proton ENDOR experiments have been conducted on the nonheme iron center from the protein nitrile hydratase. These experiments show that the transient ENDOR signal response exhibits a complex response with multiple phases in the time evolution of the ENDOR signal. Both increases and decreases in the passage-mode EPR signals are observed at different times following the RF pulse that induces an ENDOR transition. A simple model based on a packet-shifting ENDOR mechanism for a nonadiabatic passage EPR signal is proposed. This model describes many of the features seen in the transient ENDOR experiments and provides new insight into the traditional Feher-style ENDOR measurements. This new model shows that a packet-shifting mechanism can account for many of the “negative ENDOR” effects commonly seen in Feher-style ENDOR, which suggests that more exotic ENDOR mechanisms may not be required to explain these observations.     

Combining steady-state and dynamic methods for determining absolute signs of hyperfine interactions: pulsed ENDOR Saturation and Recovery (PESTRE)

The underlying causes of asymmetric intensities in Davies pulsed ENDOR spectra that are associated with the signs of the hyperfine interaction are reinvestigated. The intensity variations in these asymmetric ENDOR patterns are best described as shifts in an apparent baseline intensity that occurs dynamically following on-resonance ENDOR transitions. We have developed an extremely straightforward multi-sequence protocol that is capable of giving the sign of the hyperfine interaction by probing a single ENDOR transition, without reference to its partner transition. This technique, Pulsed ENDOR Saturation and Recovery (PESTRE) monitors dynamic shifts in the 'baseline' following measurements at a single RF frequency (single ENDOR peak), rather than observing anomalous ENDOR intensity differences between the two branches of an ENDOR response. These baseline shifts, referred to as dynamic reference levels (DRLs), can be directly tied to the electron-spin manifold from which that ENDOR transition arises. The application of this protocol is demonstrated on (57)Fe ENDOR of a 2Fe-2S ferredoxin. We use the (14)N ENDOR transitions of the S = 3/2[Fe(II)NO](2+) center of the non-heme iron enzyme, anthranilate dioxygenase (AntDO) to examine the details of the relaxation model using PESTRE.     

Absolute signs of hyperfine coupling constants as determined by pulse ENDOR of polarized radical pairs

A novel method that allows the determination of absolute signs of hyperfine coupling constants in polarized radical pair (RP) pulse electron-nuclear double resonance (ENDOR) spectra is presented, The variable mixing time (VMT) ENDOR method used here leads to a separation of ENDOR transitions originating from different electron spin manifolds by employing their dependence on the time-dependent parameters of the pulse sequence. The simple kinetic model of the RP VMT ENDOR experiment shows very good agreement with the experiments performed on the P ₇₀₀ ^.+ A ₁ ^.- RP in photosystem I. This method relies on the selective excitation of absorptive or emissive lines of one radical in the RP EPR spectrum and therefore requires high spectral resolution. This condition was fulfilled for the system studied at the low-field edge of the RP EPR spectrum obtained at Q-band. The method presented here has a very high sensitivity and does not require any equipment additional to the one used for RP pulse ENDOR. The VMT ENDOR method offers the possibility for selective suppression of signals from different electron spin manifolds.     

Local structure of titanium pair centers in SrF2 crystals: EPR and ENDOR spectroscopic studies

The local structure of titanium pair centers in SrF₂: Ti crystals is investigated using electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. It is found that titanium pair centers with spin moment S=2 and tetragonal symmetry of the magnetic properties are formed in SrF₂: Ti cubic crystals under certain growth conditions and during annealing. The tensor components of the fine and ligand hyperfine structures in the EPR and ENDOR spectra are determined. A model of the Ti⁺-Ti³⁺ paramagnetic dimer is proposed. This model provides an adequate interpretation of both the ferromagnetic nature of the exchange interaction and the observed displacements of four ligands in the first coordination sphere of titanium impurity ions in directions perpendicular to the impurity ion-ligand bonds.     

Quantitative characterization of the Mn2+ complexes of ADP and ATPγS by W-band ENDOR

W-band (95 GHz) pulsed electron nuclear double resonance (ENDOR) measurements were carried out to determine quantitatively the first coordination shell of Mn²⁺ with ADP and ATPγS. The intensity of the ENDOR effect was used for counting the number of equivalent phosphate oxygens and water ligands. Titration curves for determining the binding constant of Mn²⁺. ADP were obtained using the intensity of the X-band EPR spectrum and the³¹P ENDOR effect. Both curves gave the same binding constant showing that phosphate ligand counting is plausible, provided that an appropriate reference is available. The comparison of the³¹P ENDOR effect of the 1:1 ADP and ATPγS complexes shows that two phosphates are coordinated in both; while in ADP they are equivalent, in ATPγS they are slightly different. The reference system for water ligand counting was Mn(H₂O) ₆ ²⁺ in a H₂O-D₂O mixture. The results show a smaller error for the²H ENDOR effect, compared to the¹H ENDOR effect. Unlike the³¹P ENDOR effect, the¹H ENDOR effect dependence on [ADP] in the titration experiments showed that it is sensitive to variations in the zero-field splitting, which in turn alters the contributions of transitions other than the ‖?1/2>?‖1/2>. This results in a larger error in the determination of the number of water ligands.     

Measurement of polarization and triple-product correlations in B-->phiK* decays

We present measurements of decay amplitudes and triple-product correlations in B-->phiK* decays based on 253 fb(-1) of data recorded at the Upsilon(4S) resonance with the Belle detector at the KEKB e(+)e(-) storage ring. The decay amplitudes for the three different helicity states are determined from the angular distributions of final-state particles. The longitudinal polarization amplitudes are found to be 0.45 +/- 0.05 +/- 0.02 for B0-->phiK(*0) and 0.52 +/- 0.08 +/- 0.03 for B+ -->phiK(*+) decays. CP- and T-odd CP-violating triple-product asymmetries are measured to be consistent with zero.     

Cyclotron resonance in lead —I: Tipping effect of magnetic field

The cyclotron resonances in lead in field tipped geometry have been observed for large tipping angles up to 40° from the sample surfaces of the (111) and (100) planes. In addition to the resonance of the orbit ζ on a cylindrical arm of the electron Fermi surface, two new series of resonances, ζ^A and ζ^B have been found, of which the clotron masses are very close to that of ζ but which differ slightly in tipping angle dependence. The mass of ζ^A is dependent on microwave frequency, so that ζ^A is attributed to the Doppler-shifted cyclotron resonance of a non-stationary orbit near, ζ, whose location is discussed in relation to the Fermi surface model of Van Dyke. In field geometry normal to the (100) surface, two series of resonances have been observed, which are characterized as the extinction of even numbered harmonic resonances. This effect arises from the skipping orbit which has a trajectory topologically similar to a baseball seam in real space. One of these series is attributed to the orbit v around the junction of four electron arms.     

Local31P and distant31P and195Pt ENDOR studies of powdered samples of Bis(O,O′-disubstituted-dithiophosphato)copper(II) complexes magnetically diluted in the corresponding Pd(II) and Pt(II) host lattices

ENDOR studies on bis(dithiophosphato)copper(II) complexes magnetically diluted in the corresponding Pd(II) and Pt(II) host lattices performed with the use of the method of “polycrystalline ENDOR crystallography” are reported. In these samples well resolved local³¹P (A_iso ca. 29 MHz and A_aniso ca. 0.9 MHz) as wel1 as distant³¹P (A _iso ca. 1.3 and 5.5 MHz and A_aniso ca. 0.2 and 0.4 MHz) and¹⁹⁵Pt (A_iso ca. 3.1 MHz and A_aniso ca. 0.2 MHz) ENDOR transitions are recorded. It is shown that the directions of the main values of A_aniso for all local³¹P and distant³¹P and¹⁹⁵Pt ENDOR transitions are parallel. Comparison of these results with those reported about the same complexes but diluted in other host lattices shows that there is no difference in the EPR and local³¹P ENDOR parameters thus suggesting that the structure of the paramagnetic complex remains unchanged. It is found that distant ENDOR transitions appear only in the case when the host lattice contains one molecule in the unit cell, i.e., when all molecules are parallel to each other. Using the obtained data from local and distant³¹P ENDOR transitions some structural features of Cu(dtp)₂ as well as Pd(dtp)₂ and Pt(dtp)₂ complexes are found for the first time.