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In the high-frequency ENDOR experiments, the hyperfine (HF) interaction between the unpaired electron of the shallow donor or shallow acceptor and the nuclear spins of the Coulombic center and the surrounding atoms is determined, which is then translated into the spin density of the electronic wave function at the various atomic positions. The results of studying the spatial distribution of wave functions for shallow donors in ZnO, AgCl, AlN, and SiC crystals, ZnO-based nanostructures, and shallow boron acceptors in SiC will be presented. The change of the electronic wave function of a shallow donor in ZnO quantum dots (QDs) when entering the regime of quantum confinement by using the nuclear as probes has been observed. The model, based on the effective mass approximation (EMA), that describes a 1s-like wave function with the Bohr radius of ~ 1.5 nm for distant shells was tested. The EMA does not yield an appropriate description of the electronic wave function when the radius of the QD is reduced below the Bohr radius. The direct reconstruction of the wave function of the intrinsic shallow electronic center (SEC) and self-trapped excitons in AgCl was presented. The SEC was suggested to be an electron that is shallowly trapped by two adjacent silver ions on a single cationic site (split-interstitial position), so-called "latent image" in silver halides. The shallowly trapped electron of the STE is shown to behave like a hydrogen 1s electron, centered on the Ag+ lattice position, with a Bohr radius r0 = 1.51 nm that is in agreement with Bohr radius of SEC (r0 = 1.66 nm). For SEC in AgBr, r0 = 2.48 nm. It was demonstrated that dynamic nuclear polarization of nuclear spins due to hyperfine interactions with ligand nuclei can be achieved in ZnO (and based QDs) and AgCl by saturating the high-frequency EPR transition of a shallow donor at low temperatures corresponding to a high Boltzmann factor. Several types of shallow donors were indicated in AlN crystals: (i) affected by the DX-relaxation and (ii) with normal behavior. The strong HF interaction for light-induced SD in AlN support the assignment to the impurity in anionic sublattice (e.g. oxygen in N position). At the same time, a shallow donor with normal behavior can belong to Si or C in the Al position. The electronic structure of shallow donors and shallow acceptors in silicon carbide was investigated by the ENDOR method. The spin density of the N donor corresponding to the observed ENDOR lines was established to be p like in character and located mainly on the Si atoms for the k site in 4H-SiC, whereas for the three sites in 6H-SiC the spin density is s-like in character and located mainly on the C atoms. An explanation for the difference in the electronic wave function of the N donor in 4H-SiC and 6H-SiC can be found in the large difference in the band structure of the two polytypes and in the position of the minima in the Brillouin Zone. The electronic density for shallow B acceptor substituting Si in the k position is distributed in an ellipsoidal shape with the main symmetry axis making an angle of 70° with the c axis, i.e., along the direction of the B–C with main spin density. [ABSTRACT FROM AUTHOR]

Silver halides have unique features in solid state physics because their properties are considered to be of borderline nature between ionic and covalent bonding. In AgCl, the self-trapped hole (STH) is centered and partly trapped in the cationic sublattice, forming an Ag ion inside of a (AgCl) complex as a result of the Jahn-Teller distortion. The STH in AgCl can capture an electron from the conduction band forming the self-trapped exciton (STE). Recent results of a study of STE by means of high-frequency electron paramagnetic resonance, electron spin echo, electron-nuclear double resonance (ENDOR) and optically detected magnetic resonance (ODMR) are reviewed. The properties of the STE in AgCl crystals, such as exchange coupling, the ordering of the triplet and singlet sublevels, the dynamical properties of the singlet and triplet states, and the hyperfine interaction with the Ag and Cl (Br) nuclei are discussed. Direct information about the spatial distribution of the wave function of STE unpaired electrons was obtained by ENDOR. From a comparison with the results of an ENDOR study of the shallow electron center and STH, it is concluded that the electron is mainly contained in a hydrogen-like 1 s orbital with a Bohr radius of 15.1 ± 0.6 Å, but near its center the electron density reflects the charge distribution of the hole. The hole of the STE is virtually identical to an isolated STH center. For AgCl nanocrystals embedded into the KCl crystalline matrix, the anisotropy of the g-factor of STE and STH was found to be substantially reduced compared with that of bulk AgCl crystals, which can be explained by a considerable suppression of the Jahn-Teller effect in nanoparticles. A study of ODMR in AgBr nanocrystals in KBr revealed spatial confinement effects and allowed estimating the nanocrystal size from the shape of the ODMR spectra. [ABSTRACT FROM AUTHOR]

Electron paramagnetic resonance (EPR) and related spectroscopic tools remain among the most important probes of structure and function of natural photosynthetic systems. Indeed, the challenging questions in the study of photosynthesis have to a great extent dictated the directions taken in the development of EPR and associated spectroscopies. In this overview we demonstrate, with recent examples from our laboratories, the potential of high-frequency and time-resolved EPR spectroscopy to reveal unique information about electron transfer processes and the structure of photosynthetic systems. A common feature of these experiments is that they probe hyperfine interactions of the spincorrelated radical pair. Thus, the analysis of the results requires consideration of three interacting spins: two correlated electron spins with one nuclear spin. The results illustrate the importance of resolving nuclear hyperfine structure for obtaining details of structure-function relationships in photosynthetic electron transfer. [ABSTRACT FROM AUTHOR]

A complete theoretical treatment of the new effect observed in high-field (HF) time-resolved electron-nuclear double resonance (ENDOR) spectra of the spin-correlated radical pair (SCRP) state is presented here. This effect was recently reported for the transient charge-separated state PQ in purple photosynthetic reaction center proteins. One characteristic feature of this new phenomenon is the presence of specific, derivative-type lines in the ENDOR spectra. These lines can be explained by taking into account both a correlation between the electron spins of the photogenerated radical pairs and weak spin-spin interactions within these pairs. This correlation separates the emissive and absorptive lines and results in a differential effect. This effect is enhanced at HF, thus simplifying the analytical description of spectral structure, symmetry features, and interaction parameter dependence. The theoretical analysis presented here demonstrates that only particular nuclei which are essentially coupled to both correlated electron spins contribute to the derivative spectra. The differential effect in SCRP ENDOR manifests remarkable sensitivity to very small “secondary” hyperfine interactions that are usually unresolved in conventional thermalized ENDOR spectra. Application of this theory to experimental SCRP ENDOR spectra will offer a unique look at the internal structure of supramolecular complexes and provide a novel approach for probing electron transfer pathways in natural and artificial photosynthetic assemblies. [ABSTRACT FROM AUTHOR]

In this work D-band pulsed electron paramagnetic resonance was used to record the field-sweep spectra of several Gd3+ complexes in glassy water-methanol solutions. These spectra were analyzed by a specially developed stochastic superposition model that predicted the essential features of the distribution of the crystal field interaction (CFI) parameters in glassy systems. As a result of this analysis, the CFI distributions for the studied complexes were evaluated. The D-band Mims1H electron-nuclear double resonance spectra were free from CFI-related distortions, which allowed us to accurately determine the hyperfine interaction (HFI) parameters for water ligand protons and to unequivocally establish that the HFI distribution is solely related to the distribution of the Gd−H distances. [ABSTRACT FROM AUTHOR]

Spin-correlated radical pairs are the short-lived intermediates of the primary energy conversion steps of photosynthesis. In this paper, we develop a comprehensive model for the spin-polarized electron paramagnetic resonance (EPR) spectra of these systems. Particular emphasis is given to a proper treatment of the alignment of the photosynthetic bacteria by the field of the EPR spectormeter. The model is employed to analyze time-resolved W-band (94 GHz) EPR spectra of the secondary radical pair PA in photosystem I formed by photoexcitation of the deuterated and15N-substituted cyanobacterium Synechococcus lividus. Computer simulations of the angular-dependent EPR spectra of P700/+A1/− provide values for the order parameter of the cyanobacterial cells and for the orientation of the membrane normal in a molecular reference system. The order parameter from EPR compares favorably with corresponding data from electron microscopy obtained for the S. lividus cells under similar experimental conditions. It is shown that high-field EPR of a magnetically aligned sample in combination with the study of quantum beat oscillations represents a powerful structural tool for the short-lived radical pair intermediates of photosynthesis. [ABSTRACT FROM AUTHOR]

Time-resolved high-frequency electron paramagnetic resonance (EPR) spectroscopy was applied to study the structure and dynamics of the electron transfer pathways in the photosynthetic RC proteins. When the spin-polarized EPR spectra are recorded at the high field, the singlet-triplet mixing in the radical pairs becomes faster due to the increase of Zeeman interaction, and a sequential electron transfer polarization model, which includes both the primary and secondary radical pairs, should be considered. Application of the sequential electron transfer polarization model for the interpretation of the bacterial RC proteins with a “slow” electron transfer rate reveals the importance of the protein dynamics. It was shown that the reorganization energy for the electron transfer process between PH−QA and PHQ, but not the change in the structure of the donor-acceptor complex, is a dominant factor that alters the electron transfer rate. The relaxation data, obtained in the delay after laser flash experiment, have been used to estimate the magnetic interaction in the weakly coupled radical pair. High-frequency spin-polarized EPR spectra allow the quantitative characterization of isotopically labeled quinone exchange in the PS I reaction center proteins. [ABSTRACT FROM AUTHOR]

A pulsed 2-mm band EPR spectrometer is described. The perspectives of 2-mm band EPR are comprehensively discussed. [ABSTRACT FROM AUTHOR]