Electron Nuclear Double Resonance Experiments Research Articles

Determination of the g Tensors for the Dominant Stable Radicals in X-Irradiated β-d-Fructose Single Crystals

In spite of recent successful identifications of radicals produced after X-ray irradiation at 10 and 77 K in beta-D-fructose, the structure of the two stable radicals dominating the electron paramagnetic resonance (EPR) spectrum after room temperature irradiation is still unclear. Based on the agreement between proton hyperfine (HF) tensors obtained in electron nuclear double resonance (ENDOR) experiments and the results of single molecule density functional calculations, a model for these radicals, involving OH abstraction at the C2 ring position, had previously been proposed, but this assignment could not be confirmed when the radical was embedded in a crystal environment. In this paper, we therefore provide additional experimental information for these radicals. First, their g tensors are determined from angular dependent ENDOR-induced EPR experiments. The relatively large anisotropy of these tensors is indicative of delocalization of the unpaired electron onto a neighboring oxygen atom. Second, EPR spectra of fructose powders, selectively enriched in (13)C on various ring positions, are presented, demonstrating that the HF interaction with the carbon atom C3 is larger than with the C2. Combining the g tensor, proton and (13)C HF data, we conclude that the structure of the stable radicals differs strongly from that of intact molecules and that further advanced quantum chemical modeling will be required to fully identify them.

ENDOR and HYSCORE analysis and DFT-assisted identification of the third major stable radical in sucrose single crystals X-irradiated at room temperature

Recently, the chemical structure of two of the three major stable radicals (T2 and T3) produced in sucrose single crystals by X-irradiation at room temperature was identified by comparing Density Functional Theory (DFT) calculations of Electron Magnetic Resonance parameters with experimental results [H. De Cooman, E. Pauwels, H. Vrielinck, E. Sagstuen, F. Callens and M. Waroquier, J. Phys. Chem. B, 2008, 112, 7298-7307]. Ambiguities concerning an unusual proton hyperfine coupling (HFC) tensor prevented the identification of the third major stable radical (T1). In the present work, experimental results of continuous wave Electron Nuclear Double Resonance experiments on sucrose single crystals and Hyperfine Sublevel Correlation Spectroscopy experiments on sucrose powder are presented that lift these remaining ambiguities. Using the final set of experimental HFC tensors and employing advanced DFT calculations, the chemical structure of the T1 radical is established: an allylic-type radical with approximately half of the spin density localised on the C2' carbon of the fructose unit, involving glycosidic bond cleavage at the fructose side and a concerted formation of a carbonyl group at the C1' carbon. The electronic structure of the T1 radical is discussed in more detail by means of additional DFT calculations, yielding a better understanding of the peculiar properties of the unusual proton HFC tensor mentioned above.

Structure and bonding of [VIVO(acac)2] on the surface of AlF3 as studied by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy

Well defined isolated [V(IV)O(acac)(2)] surface complexes have been prepared on aluminium trifluoride, alpha-AlF(3), as solid support by equilibrium adsorption from liquid solution. The paramagnetic vanadium(iv) surface complexes were studied by pulsed electron spin resonance spectroscopy in combination with quantum chemical calculations using density functional theory. (19)F and (27)Al ligand hyperfine interactions with the nuclei of the AlF(3) support observed by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy experiments verify the direct chemical bonding between the vanadium and a surface fluorine atom. Detailed analysis of the ligand hyperfine couplings supported by quantum chemical calculations indicates that the axial position of [V(IV)O(acac)(2)]trans to the oxo ligand is bound directly to a terminal fluorine atom of the support. Analysis of the (1)H ligand hyperfine interaction revealed that an acidic H(+) of the AlF(3) surface protonated a donor oxygen of the acetylacetone ligand in the surface complex.

General and efficient simulation of pulse EPR spectra

We present a rather general and efficient method of simulating electron-spin echo spectra for spin systems where the microwave frequency does not simultaneously excite EPR transitions that share a common level. The approach can handle arbitrary pulse sequences with microwave pulses of arbitrary length and strength. The signal is computed as a sum over signals from the electron coherence transfer pathways contributing to the detected echo. For each pathway, amplitudes and frequencies of the signal components are computed and used to construct a spectral histogram from which the time-domain signal is obtained. For multinuclear spin systems, the nuclear subspace is factorized to accelerate the computation. The method is also applicable to high electron spin systems with significant zero-field splitting and to pulse electron-nuclear double resonance experiments. The method is implemented in the software package EasySpin, and several illustrative calculations are shown.

Schonland ambiguity in the electron nuclear double resonance analysis of hyperfine interactions: Principles and practice

For the analysis of the angular dependence of electron paramagnetic resonance (EPR) spectra of low-symmetry centres with S = 1/2 in three independent planes, it is well-established—but often overlooked—that an ambiguity may arise in the best-fit g ↔ tensor result. We investigate here whether a corresponding ambiguity also arises when determining the hyperfine coupling (HFC) A ↔ tensor for nuclei with I = 1/2 from angular dependent electron nuclear double resonance (ENDOR) measurements. It is shown via a perturbation treatment that for each set of M S ENDOR branches two best-fit A ↔ tensors can be derived, but in general only one unique solution simultaneously fits both. The ambiguity thus only arises when experimental data of only one M S multiplet are used in analysis or in certain limiting cases. It is important to realise that the ambiguity occurs in the ENDOR frequencies and therefore the other best-fit result for an ENDOR determined A ↔ tensor depends on various details of the ENDOR experiment: the M S state of the fitted transitions, the microwave frequency (or static magnetic field) in the ENDOR measurements and the rotation planes in which data have been collected. The results are of particular importance in the identification of radicals based on comparison of theoretical predictions of HFCs with published literature data. A procedure for obtaining the other best-fit result for an ENDOR determined A ↔ tensor is outlined.

55Mn-ENDOR of the S2-state multiline signal of Photosystem II from Thermosynechococcus elongatus

Pulse EPR and 55Mn-ENDOR (electron nuclear double resonance) experiments at 34 GHz (Q-band) were performed on the S2 state of the OEC (oxygen-evolving complex) in PSII (Photosystem II) from Thermosynechococcus elongatus. The ENDOR spectra are discussed with respect to earlier data obtained from X- (9 GHz) and Q-band experiments on PSII preparations from spinach with and without the addition of methanol.

A multifrequency high-field pulsed electron paramagnetic resonance/electron-nuclear double resonance spectrometer

We describe a pulsed electron paramagnetic resonance spectrometer operating at several frequencies in the range of 110-336 GHz. The microwave source at all frequencies consists of a multiplier chain starting from a solid state synthesizer in the 12-15 GHz range. A fast p-i-n-switch at the base frequency creates the pulses. At all frequencies a Fabry-Perot resonator is employed and the pi/2 pulse length ranges from approximately 100 ns at 110 GHz to approximately 600 ns at 334 GHz. Measurements of a single crystal containing dilute Mn(2+) impurities at 12 T illustrate the effects of large electron spin polarizations. The capabilities also allow for pulsed electron-nuclear double resonance (ENDOR) experiments as demonstrated by Mims ENDOR of (39)K nuclei in Cr:K(3)NbO(8).

Identification of shallow Al donors in Al-doped ZnO nanocrystals: EPR and ENDOR spectroscopy

Electron paramagnetic resonance and electron-nuclear double resonance (ENDOR) experiments on ZnO nanoparticles doped with Al reveal the presence of shallow, effective-masslike donors related to substitutional Al atoms. The shallow character of the Al donor is evidenced by the multitude of ENDOR transitions of the $^{67}\text{Z}\text{n}$ nuclear spins and by the hyperfine interaction of 1.45 MHz of the $^{27}\text{A}\text{l}$ nuclear spin, which is much smaller than for atomic aluminum. The electric-field gradients at the Al and Zn atoms are found to be nearly the same, which supports the contention that the Al atom is located at a Zn position.

Jahn–Teller Distortion of the Zinc Vacancy in ZnGeP2

A symmetry analysis and a simple dangling bond model are presented for the VZn− in ZnGeP2, identifying a possible Jahn–Teller distortion mechanism which could naturally explain the localization of the defect wavefunction on two of the nearest-neighbouring P atoms, as deduced for the electron nuclear double resonance experiments.

Multifrequency EPR analysis of the positive polaron in I2-doped poly(3-hexylthiophene) and in poly[2-methoxy-5-(3,7-dimethyloctyloxy)]-1,4-phenylenevinylene

The W-band continuous-wave electron paramagnetic resonance (EPR) analysis of chemically induced polarons in drop-cast and spin-coated polyphenylenevinylene-type and polythiophene-type polymer films reveals rhombic g tensors in both cases. The dependence of the W-band EPR signals on the orientation of the spin-coated films with respect to the magnetic field indicates a high degree of backbone alignment with the substrate and allows a partial assignment of the g tensor orientation. The derived molecular orientations of the polymer chains in the spin-coated films show clear differences between the two types of polymers. The proton hyperfine interactions obtained from X-band HYSCORE (hyperfine sublevel correlation) and Q- and W-band pulsed ENDOR (electron-nuclear double resonance) experiments are interpreted in terms of earlier theoretical studies on the extension of the polarons.

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.

Studies of the Mo(V) center of the Y343F mutant of human sulfite oxidase by variable frequency pulsed EPR spectroscopy

The Mo(V) forms of the Tyr343Phe (Y343F) mutant of human sulfite oxidase (SO) have been investigated by continuous wave (CW) and variable frequency pulsed EPR spectroscopies as a function of pH. The CW EPR spectrum recorded at low-pH (∼6.9) has g-values similar to those known for the low-pH form of the native vertebrate SO ( original lpH form); however, unlike the spectrum of original lpH SO, it does not show any hyperfine splittings from a nearby exchangeable proton. The detailed electron spin echo (ESE) envelope modulation (ESEEM) and pulsed electron-nuclear double resonance (ENDOR) experiments also did not reveal any nearby protons that could belong to an exchangeable ligand at the molybdenum center. These results suggest that under low-pH conditions the active site of Y343F SO is in the “blocked” form, with the Mo(V) center coordinated by sulfate. With increasing pH the EPR signal from the “blocked” form decreases, while a signal similar to that of the original lpH form appears and becomes the dominant signal at pH >9. In addition, both the CW EPR and ESE-detected field-sweep spectra reveal a considerable contribution from a signal similar to that usually detected for the high-pH form of native vertebrate SO ( original hpH form). The nearby exchangeable protons in both of the component forms observed at high-pH were studied by the ESEEM spectroscopy. These results indicate that the Y343F mutation increases the apparent p K a of the transition from the lpH to hpH forms by ∼2 pH units.

Donor-acceptor pairs in the confined structure ofZnOnanocrystals

The electron paramagnetic resonance signal of an exchange-coupled pair consisting of a shallow interstitial Li donor and a deep Na-related acceptor has been identified in $\mathrm{ZnO}$ nanocrystals with radii smaller than $1.5\phantom{\rule{0.3em}{0ex}}\mathrm{nm}$. From electron nuclear double resonance experiments it is concluded that the deep Na-related acceptor is located at the interface of the $\mathrm{ZnO}$ core and the $\mathrm{Zn}(\mathrm{OH}{)}_{2}$ capping layer, while the Li donor is in the $\mathrm{ZnO}$ core.

Davies electron-nuclear double resonance revisited: Enhanced sensitivity and nuclear spin relaxation

Over the past 50 years, electron-nuclear double resonance (ENDOR) has become a fairly ubiquitous spectroscopic technique, allowing the study of spin transitions for nuclei which are coupled to electron spins. However, the low spin number sensitivity of the technique continues to pose serious limitations. Here we demonstrate that signal intensity in a pulsed Davies ENDOR experiment depends strongly on the nuclear relaxation time T(1n), and can be severely reduced for long T(1n). We suggest a development of the original Davies ENDOR sequence that overcomes this limitation, thus offering dramatically enhanced signal intensity and spectral resolution. Finally, we observe that the sensitivity of the original Davies method to T(1n) can be exploited to measure nuclear relaxation, as we demonstrate for phosphorous donors in silicon and for endohedral fullerenes N@C(60) in CS(2).

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.

Electron–nuclear double resonance and dynamic nuclear polarization in GaAs in the regime of the quantum Hall effect

Electron spin resonance (ESR) and electron-nuclear double resonance experiments were performed in the 2D electron systems of GaAs/Al x Ga 1− x As quantum well and heterojunction samples in the vicinity of the unity filling factor in the regime of the quantum Hall effect. As is well known, the ESR response is strongly affected by the local nuclear fields induced by dynamic nuclear polarization. The peculiar resistance responses resulting from dynamic nuclear polarization and NMR were numerically simulated on the basis of the rate equation for the Zeeman order of nuclei in the vicinity of the 2D electron system. The simulations, which include the nuclear spin diffusion, provide an opportunity to visualize the propagation of the nuclear spin polarization into the Al x Ga 1− x As barriers of the quantum wells.

Unambiguous Determination of theg-Matrix Orientation in a Neutral Flavin Radical by Pulsed Electron−Nuclear Double Resonance at 94 GHz

The recent observation of photoinduced radical pairs comprising a flavin radical and an oxidized amino acid residue in various blue-light-sensitive proteins has highlighted the need to gain a more complete understanding of the electronic structure of flavin radicals. In particular, precise knowledge of the anisotropy of the Zeeman interaction quantified by the g-tensor is necessary for attaining an unambiguous identification of flavin radicals by electron paramagnetic resonance (EPR). In a recent study of a protein-bound neutral flavin radical, we have determined the principal values of the g-tensor using high-frequency/high magnetic field EPR performed at 360 GHz/12.8 T. However, in those experiments, the orientation of the principal axes of g could not be unambiguously established with respect to the molecular frame of the isoalloxazine moiety. In this contribution we resolve this ambiguity by pulsed electron-nuclear double resonance (ENDOR) at 95 GHz/3.5 T (W-band). At such high values of the microwave frequency and the magnetic field, the g anisotropy provides improved spectral resolution compared to an ENDOR experiment performed at conventional 9.5 GHz/0.35 mT (X-band). This enables one to utilize Zeeman magnetoselection to obtain single-crystal-like data from disordered samples in frozen solution. Experiments exploiting this orientation selection have allowed us to use the hyperfine coupling of the methyl protons at C(8alpha) of the isoalloxazine ring to determine the angle between the molecular frame and the principal axes of g. Quite surprisingly, the g-tensor in FADH* is not oriented as one would have expected for a 1,3-semibenzoquinone radical. For the latter, the X-axis of g commonly bisects the smaller angle between the two axes along the C=O bonds. In FADH*, the large spin density on N(5) and C(4a) apparently contributes to a significant (44 degrees ) reorientation of the g-tensor axes.

Pulsed ENDOR Study of Cu(I)−NO Adsorption Complexes in Cu−L Zeolite

The local environments of Cu(I)-NO adsorption complexes formed in zeolites Cu-L and Cu-ZSM-5 were studied by electron spin resonance (ESR), pulsed electron nuclear double resonance (ENDOR), and hyperfine sublevel correlation spectroscopy (HYSCORE). Cu(I)-NO complexes have attracted special interest because they are important intermediates in the catalytic decomposition of nitric oxide over copper exchanged zeolites. Recently, detailed structures of the complexes in Cu-ZSM-5 zeolites, O2-Al-O2-Cu(I)-NO, have been proposed on the basis of quantum chemical calculations (Pietrzyk, et al. J. Phys. Chem. B 2003, 107, 6105. Dedecek, et al. Phys. Chem. Chem. Phys. 2002, 4, 5406). 27Al pulsed ENDOR and HYSCORE experiments allowed the hyperfine coupling parameters of an aluminum nuclei found in the vicinity of the Cu(I)-NO complex formed in zeolite Cu-L to be estimated. The data indicate that the aluminum atom is located in the third coordination sphere of the adsorbed NO molecule in agreement with the suggested geometry of the adsorption sites. Broad distributions of aluminum nuclear quadrupole and hyperfine coupling parameters and short electron spin relaxation times of the Cu(I)-NO species prevented the determination of the 27Al hyperfine couplings for zeolite Cu-ZSM-5.

Spin distribution in neutral polyene radicals: Pariser–Parr–Pople model studied with the density matrix renormalization group method

The geometries and pi electron spin distributions induced by neutral soliton defects in trans-polyacetylene radicals (from C(7)H(9) to C(49)H(51)) are studied using Pariser-Parr-Pople (PPP) model, solved by the density matrix renormalization group (DMRG) method. Comparisons with other quantum chemical methods as well as the experimental observations on heptatrienyl (C(7)H(9)) and nonatetraenyl (C(9)H(11)) radical species show that the semiempirical PPP method is in the list of the very few theories that can give correct description of the spin distributions for such extended pi-conjugated systems. By virtue of DMRG's power in dealing with large one-dimensional systems, we predicted that the half-width of a neutral spin soliton in polyacetylene is about 14 atoms, and the spin distributions in the center of the soliton is calculated as rho(0)=0.25, rho(1)=-0.12 with rho(1)rho(0)=-0.48, rho(-)rho(+)=-0.52, which agree well with the results from electron-nuclear double resonance experiments.

Magnetic resonance study of Cr 3+ and Fe 3+ centers in hexagonal Cs 2 NaAlF 6 and Cs 2 NaGaF 6 crystals

In the search for new solid-state laser materials, hexagonal Cs2NaAlF6 and Cs2NaGaF6 crystals doped with Cr3+ ions have been synthesized under hydrothermal conditions. Fe3+ ions have been found as unintentional impurities in these materials. Electron paramagnetic resonance and electron nuclear double resonance experiments of these elpasolite crystals have allowed unambiguously identifying the lattice sites for both Cr3+ and Fe3+ ions, by observing the interaction of the unpaired electrons with the nearest 19F and 23Na nuclei. The correlation between spin Hamiltonian parameters and crystallographic data is discussed. The results support the earlier identification of the Cr3+ centers in these crystals from optical measurements. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)