Dipolar Spin-spin Interactions Research Articles

Conducting a three-pulse DEER experiment without dead time: A review

Double electron-electron resonance spectroscopy (DEER, also known as PELDOR) is used to study spin-spin dipolar interactions between spin labels, at the nanoscale range of distances. The DEER effect is obtained as a signal generated by echo-forming microwave (mw) pulses with an additional mw pump pulse applied at a different frequency. It is important to carry out measurements without artefacts induced by overlap of the pulses in the time scale. Such an experiment without the dead-time effect is achieved using the 4-pulse (4p) DEER method. The analysis of the literature performed here shows however that the 3-pulse (3p) DEER can also be free of the dead time problem, for which there are two possibilities. The first occurs using a specially designed bimodal resonator, for which the two frequencies are completely decoupled. The second possibility, which can be implemented for any commercial spectrometer, involves the signal correction based on an additional “blank” measurement with the pump pulse applied outside the EPR resonance. A detailed comparison of the 3p and 4p DEER data obtained previously by Milov et al. [Appl. Magn. Reson. 41 (2011) 59–67] shows that 3p and 4p approaches give similar results. The advantages of the 3p DEER techniques are discussed.

Intermolecular contributions, filtration effects and signal composition of SIFTER (single-frequency technique for refocusing).

To characterize structure and molecular order in the nanometre range, distances between electron spins and their distributions can be measured via dipolar spin-spin interactions by different pulsed electron paramagnetic resonance experiments. Here, for the single-frequency technique for refocusing dipolar couplings (SIFTER), the buildup of dipolar modulation signal and intermolecular contributions is analysed for a uniform random distribution of monoradicals and biradicals in frozen glassy solvent by using the product operator formalism for electron spin . A dipolar oscillation artefact appearing at both ends of the SIFTER time trace is predicted, which originates from the weak coherence transfer between biradicals. The relative intensity of this artefact is predicted to be temperature independent but to increase with the spin concentration in the sample. Different compositions of the intermolecular background are predicted in the case of biradicals and in the case of monoradicals. Our theoretical account suggests that the appropriate procedure of extracting the intramolecular dipolar contribution (form factor) requires fitting and subtracting the unmodulated part, followed by division by an intermolecular background function that is different in shape. This scheme differs from the previously used heuristic background division approach. We compare our theoretical derivations to experimental SIFTER traces for nitroxide and trityl monoradicals and biradicals. Our analysis demonstrates a good qualitative match with the proposed theoretical description. The resulting perspectives for a quantitative analysis of SIFTER data are discussed.

Quintet Dinitrenes with Negative Zero-Field Splitting: Effect of Spin-Orbit Coupling on the Sign of Magnetic Anisotropy.

We report on W-band EPR and quantum chemical investigation of novel organic tetraradicals with negative axial zero-field splitting (ZFS) parameter D. These belong to the class of quintet 1,3,5-tribromophenylene-2,4-dinitrenes bearing different substituents in position 6 of the benzene ring (1b, N3; 1c, F; 1d, CN; 1e; Cl; 1f, Br). Analysis of the W-band EPR spectrum of dinitrene 1c reveals its large negative ZFS parameter D = -0.27 cm-1. Quantum chemical calculations show that negative D gradually grows in the row of 1c(F) < 1b(N3) < 1d(CN) < 1e(Cl) < 1f(Br) dinitrenes due to decreasing of the through-space distance between the nitrene units and neighboring bromine atoms. Shorter steric N···Br distance results in the stronger contribution of the spin-orbit coupling (SOC) to the total ZFS. The sign of D depends on the interplay of three factors: (i) the angle θ between the "easy" z-axes of the dipolar spin-spin (DSS) and spin-orbit (DSOC) interaction tensors, (ii) the ratio of DSOC/DSS values, and (iii) the rhombicity parameters ESS/DSS and ESOC/DSOC. The study demonstrates in which cases organic quintet tetraradicals may have negative ZFS owing to the presence of heavy atoms at appropriate sites nearby the nitrene units and, thus, possess the bistability property as single-molecule magnets.

Light-induced pulsed dipolar EPR spectroscopy for distance and orientation analysis.

Measuring distances in biology at the molecular level is of great importance for understanding the structure and function of proteins, nucleic acids and other biological molecules and their complexes. Pulsed Dipolar Spectroscopy (PDS) offers advantages with respect to other methods as it is uniquely sensitive and specific to electronic spin centers and allows measurements in near-native conditions, comprising the in-cell environment. PDS methods measure the electron spin-spin dipolar interaction, therefore they require the presence of at least two paramagnetic centers, which are often stable radicals. Recent developments have introduced transient triplet states, photo-activated by a laser pulse, as spin labels and probes, thereby establishing a new family of techniques-Light-induced PDS (LiPDS). In this chapter, an overview of these methods is provided, looking at the chromophores that can be used for LiPDS and some of the technical aspects of the experiments. A guide to the choice of technique that can yield the best results, depending on the type of system studied and the information required, is provided. Examples of previous LiPDS studies of model systems and proteins are given. Characterization data for the chromophores used in these studies is tabulated to help selection of appropriate triplet state probes in future studies.

Photogenerated Spin-Correlated Radical Pairs: From Photosynthetic Energy Transduction to Quantum Information Science.

More than a half century ago, the NMR spectra of diamagnetic products resulting from radical pair reactions were observed to have strongly enhanced absorptive and emissive resonances. At the same time, photogenerated radical pairs were discovered to exhibit unusual electron paramagnetic resonance spectra that also had such resonances. These non-Boltzmann, spin-polarized spectra were observed in both chemical systems as well as in photosynthetic reaction center proteins following photodriven charge separation. Subsequent studies of these phenomena led to a variety of chemical electron donor-acceptor model systems that provided a broad understanding of the spin dynamics responsible for these spectra. When the distance between the two radicals is restricted, these observations result from the formation of spin-correlated radical pairs (SCRPs) in which the spin-spin exchange and dipolar interactions between the two unpaired spins play an important role in the spin dynamics. Early on, it was recognized that SCRPs photogenerated by ultrafast electron transfer are entangled spin pairs created in a well-defined spin state. These SCRPs can serve as spin qubit pairs (SQPs), whose spin dynamics can be manipulated to study a wide variety of quantum phenomena intrinsic to the field of quantum information science. This Perspective highlights the role of SCRPs as SQPs, gives examples of possible quantum manipulations using SQPs, and provides some thoughts on future directions.

Double Electron-Electron Resonance of Spin-Labeled Cholestane in Model Membranes: Evidence for Substructures inside the Lipid Rafts.

Plasma membranes are assumed to be highly compartmentalized, which is believed to be important for the membrane protein functionality. The liquid ordered-disordered phase segregation in the membranes results in nanoscale liquid-ordered assemblies-lipid rafts. Double electron-electron resonance spectroscopy (DEER, also known as PELDOR) is sensitive to spin-spin dipolar interactions between spin labels at the nanoscale range of distances. Here, DEER is applied to spin-labeled cholestane, 3β-doxyl-5α-cholestane (DChl), diluted in bilayers composed of an equimolar mixture of dioleoyl-glycero-phosphocholine (DOPC) and dipalmitoyl-glycero-phosphocholine (DPPC) phospholipids, with cholesterol (Chol) added. The DEER data allowed us to detect clustering of the DChl molecules. Their lateral distribution in the clusters in the absence of Chol was found to be random, while in the presence of Chol it became quasi-regular. DEER time traces are fairly well simulated within a simple square superlattice model. For the 20 mol % Chol content, for which at physiological temperatures, the lipid rafts are formed, the found superlattice parameter was 3.7 nm. Assuming that lipid rafts are captioned upon shock freezing at the temperature of investigation (80 K), the found regularity of DChl lateral distribution was interpreted by raft substructuring, with the DChl molecules embedded between the substructures.

Interaction of Photogenerated Spin Qubit Pairs with a Third Electron Spin in DNA Hairpins.

The designing of tunable molecular systems that can host spin qubits is a promising strategy for advancing the development of quantum information science (QIS) applications. Photogenerated radical pairs are good spin qubit pair (SQP) candidates because they can be initialized in a pure quantum state that exhibits relatively long coherence times. DNA is a well-studied molecular system that allows for control of energetics and spatial specificity through careful design and thus serves as a tunable scaffold on which to control multispin interactions. Here, we examine a series of DNA hairpins that use naphthalenediimide (NDI) as the hairpin linker. Photoexcitation of the NDI leads to subnanosecond oxidation of guanine (G) within the duplex or a stilbenediether (Sd) end-cap to give NDI•--G•+ or NDI•--Sd•+ SQPs, respectively. A 2,2,6,6-tetramethylpiperdinyl-1-oxyl (TEMPO) stable radical is covalently attached to the hairpin at varying distances from the SQP spins. While TEMPO has a minimal effect on the SQP formation and decay dynamics, EPR spectroscopy indicates that there are significant spin-spin dipolar interactions between the SQP and TEMPO. We also demonstrate the ability to implement more complex spin manipulations of the NDI•--Sd•+-TEMPO system using pulse-EPR techniques, which is important for developing DNA hairpins for QIS applications.

Relaxation time enhancement by magnetic dilution in single-molecule magnets: An ab initio study

Abstract Magnetic dilution is an effective strategy to enhance demagnetization times of Single-Molecule Magnets (SMMs). In this approach, a magnetic complex is co-crystallized with a diamagnetic analog to increase the distance between neighbor magnetic centers, diminishing the contribution of spin-spin dipolar interactions to demagnetization. In this article, we present an ab initio procedure to predict tunneling relaxation times (τ QT ) for magnetically diluted Single-Molecule Magnets. From a benchmark set of 18 mononuclear Ln III ions, it is concluded that the effect of magnetic dilution shows the same profile and a similar magnitude for all studied systems. For strongly diluted samples (i.e. 1% concentration), the model predicts and enhancement of around 4 orders of magnitude in τ QT . Typical dilution proportions of 1:10 or 1:20 are associated by a ca. 100-fold increase in relaxation time. Variations in relaxation time were analyzed for three cases where experimental information for one dilution ratio is available. Furthermore, τ QT at several magnetic ion concentrations were predicted for [Er(W 5 O 18 ) 2 ] 9− and compared with literature data. In both cases, the agreement between experiment and theory was satisfactory, finding a general quadratic dependence on relaxation time enhancement upon magnetic dilution.

Magnetic anisotropy Berry's phase

By considering the intrinsic anisotropy, present in almost all magnetic systems, as a perturbation to the usual Zeeman term, we show that the spin-spin dipolar interaction also known as zero-field splitting (ZFS) leads to an extra geometrical phase in addition to the conventional Berry's phase. Furthermore, we suggest some ways to observe the energy shift in electron paramagnetic resonance spectra due to Berry's phase and how we can separate it from the conventional Zeeman Berry's phase.One of the authors (MM) dedicates this work to the memory of his mother, Djabou Zoulikha, who died on 3 February 2019.

Ab initio calculation of the spin lattice relaxation time T1 for nitrogen-vacancy centers in diamond

We investigate the fundamental mechanism of spin phonon coupling in the negatively charged nitrogen vacancy center $(\mathrm{NV}^-)$ in diamond in order to calculate the spin lattice relaxation time $T_1$ and its temperature dependence from first principles. Starting from the dipolar spin-spin interaction between two electrons, we couple the spins of the electrons to the movements of the ions and end up with an effective spin-phonon interaction potential $V_{s-ph}$. Taking this time dependent potential as a perturbation of the system, a Fermi's golden rule expression for transition rates is obtained which allows to calculate the spin lattice relaxation time $T_1$. We simulate the color center with the Vienna Ab initio Simulation Package (VASP) to extract the figures necessary to quantify $T_1$. We investigate on the local phonon modes of the color center within the harmonic approximation using the small displacement method and extract the phononic density of states and bandstructure by diagonalizing the dynamical matrix using the phononpy package. We show that our model allows to calculate $T_1$ in good agreement with experimental observations.

Posner qubits: spin dynamics of entangled Ca9(PO4)6 molecules and their role in neural processing.

It has been suggested that 31P nuclear spins in Ca9(PO4)6 molecules could form the basis of a quantum mechanism for neural processing in the brain. A fundamental requirement of this proposal is that spins in different Ca9(PO4)6 molecules can become entangled and remain so for periods (estimated at many hours) that hugely exceed typical 31P spin relaxation times. Here, we consider the coherent and incoherent spin dynamics of Ca9(PO4)6 arising from dipolar and scalar spin-spin interactions and derive an upper bound of 37 min on the entanglement lifetime under idealized physiological conditions. We argue that the spin relaxation in Ca9(PO4)6 is likely to be much faster than this estimate.

Geometries and Dynamics of Photoinduced Electron-Hole Pairs in Polyhexylthiophene-Fullerene Systems

For developments of the organic light-energy conversion systems, it is essential to achieve efficient long-range charge-separations (CS). Light-induced electrons and holes generated by the electron-transfer (ET) reactions are thus required to escape from the electrostatic binding at the initial stage. In the natural photosynthetic reaction centers, the efficient distant CS is accomplished with ~100% efficiency by cascading the redox states by the sequential ET processes to a series of cofactors, leading to the light-to-chemical energy conversion. In contrast, the photoinduced CS at the interfaces of organic photovoltaic (OPV) cells generates electron-hole pairs, eventually achieving light-to-electricity conversion after conductions of the electron and the hole through the donor (D) and the acceptor (A) domains, respectively. However, the D/A interfaces in the OPV cells often suffer from the charge-recombination (CR) at the early stage, leading to losses of the input photon energies. Concerning the mechanism of the efficient photo-career generations in the OPV systems, role of the hot charge-transfer (CT) excitons is currently under intense debate. A recent ultrafast spectroscopic study of a polymer/fullerene (PCPDTBT/PC60BM) OPV films clearly showed that the vibrationally unrelaxed electron-hole pairs (PCPDTBT+/PC60BM-) are generated in < 50 fs before time scales of the internal conversions (IC) of the polymer excited states.[1] On the other hand, Vandewal et al.[2] have demonstrated for the several polymer:PCBM solar cells that the internal quantum efficiency (IQE) is essentially independent of the excitation energy of the lights; even if the low-energy CT band is excited, the IQE is higher than 90 % for some blend films, giving rise to very high OPV performances. This result strongly indicates that the hot CT states are not necessarily required to produce the highly separated photo-careers. To elucidate why and how the photo-carriers escape from the Coulomb binding, it is important to directly observe locations and orientations of the intermediate charges just after the CSs. Time-resolved electron paramagnetic resonance (TREPR) and pulsed EPR methods have been powerful to obtain the electron spin-spin dipolar interaction and the spin-spin exchange coupling in the photoinduced CS states and thus have been utilized to characterize the interspin distances and the electronic couplings of the transient CS states. The TREPR analyses have been useful to obtain the CS state geometries for several systems, since the electron spin polarization (ESP) as the microwave absorption (A) and the emission (E) is sensitive to the molecular conformations.[3] Recent spin polarization analyses have revealed representative geometries of the transient electron-hole pairs in the OPV blends.[4] However, the highly inhomogeneous molecular environments at the bulk-heteojunction (BHJ) interfaces induces the large special distribution in the solid-state OPV materials and would prevent us from understanding the mechanism of the charge conductions. To unveil fundamental molecular mechanisms of the light-induced charge conductions, it is highly desired to investigate the structure and dynamics of the initial photo-carriers generated in a conjugated polymer-backbone in which the intramolecular orientation and the electronic interaction are well-defined at the initial CS stage. Thus far, no study has characterized the geometry, electronic coupling and charge-conduction dynamics of the photo-carriers in a covalently linked polymer system, although the polymer-fullerene dyads were synthetized and investigated by transient spectroscopies. In this respect, we have synthesized a new series of donor-bridge-acceptor (P3HT-Phm-C60, m = 0, 1, 2, 3) linked polymers composed of regio-regular poly(3-hexylthiophene) (P3HT) as the electron donor, ful-leropyrrolidine (C60) as the acceptor and oligo-p-phenylene bridges as the spacers.[5] We have herein investigated the molecular geometries and the hole-conduction dynamics of the photoinduced intramolecular CS states by using the TREPR in tetrahydrofuran (THF) at room temperature. We clearly show that, without going through the hot CT, localized holes are generated in the conjugated polymer-backbones nearby the phenylene units by quenching triplet excitons and then undergo one-dimensional intramolecular dissocia-tions from the electrons situated at C60 in the dyads. Grancini, G.; Maiuri, M.; Fazzi, D.; Petrozza, A.; Egelhaaf, H. J.; Brida, D.; Cerullo, G.; Lanzani, G. Nat. Mater. 2013, 12, 29-33.Vandewal, K.; Albrecht, S.; Hoke, E. T.; Graham, K. R.; Widmer, J.; Douglas, J. D.; Schubert, M.; Mateker, W. R.; Bloking, J. T.; Burkhard, G. F.; Sellinger, A.; Frechet, J. M. J.; Amassian, A.; Riede, M. K.; McGehee, M. D.; Neher, D.; Salleo, A. Nat. Mater. 2014, 13, 63-68.Kobori, Y.; Miura, T. J. Phys. Chem. Lett. 2015, 6, 113-123.Kobori, Y.; Noji, R.; Tsuganezawa, S. J. Phys. Chem. C 2013, 117, 1589-1599.Miura, T.; Tao, R.; Shibata, S.; Umeyama, T.; Tachikawa, T.; Imahori, H.; Kobori, Y. J . Am. Chem. Soc. 2016, 138, 5879-5885.

Neutron spin-echo study of the critical dynamics of spin-52antiferromagnets in two and three dimensions

We report a neutron spin-echo study of the critical dynamics in the $S=5/2$ antiferromagnets MnF$_2$ and Rb$_2$MnF$_4$ with three-dimensional (3D) and two-dimensional (2D) spin systems, respectively, in zero external field. Both compounds are Heisenberg antiferromagnets with a small uniaxial anisotropy resulting from dipolar spin-spin interactions, which leads to a crossover in the critical dynamics close to the N\'eel temperature, $T_N$. By taking advantage of the $\mu\text{eV}$ energy resolution of the spin-echo spectrometer, we have determined the dynamical critical exponents $z$ for both longitudinal and transverse fluctuations. In MnF$_2$, both the characteristic temperature for crossover from 3D Heisenberg to 3D Ising behavior and the exponents $z$ in both regimes are consistent with predictions from the dynamical scaling theory. The amplitude ratio of longitudinal and transverse fluctuations also agrees with predictions. In Rb$_2$MnF$_4$, the critical dynamics crosses over from the expected 2D Heisenberg behavior for $T\gg T_N$ to a scaling regime with exponent $z = 1.387(4)$, which has not been predicted by theory and may indicate the influence of long-range dipolar interactions.

(1)H and (19)F spin-lattice relaxation and CH3 or CF3 reorientation in molecular solids containing both H and F atoms.

The dynamics of methyl (CH3) and fluoromethyl (CF3) groups in organic molecular (van der Waals) solids can be exploited to survey their local environments. We report solid state (1)H and (19)F spin-lattice relaxationexperiments in polycrystalline 3-trifluoromethoxycinnamic acid, along with an X-ray diffraction determination of the molecular and crystal structure, to investigate the intramolecular and intermolecular interactions that determine the properties that characterize the CF3 reorientation. The molecule is of no particular interest; it simply provides a motionless backbone (on the nuclear magnetic resonance(NMR) time scale) to investigate CF3 reorientation occurring on the NMR time scale. The effects of (19)F-(19)F and (19)F-(1)H spin-spin dipolar interactions on the complicated nonexponential NMRrelaxation provide independent inputs into determining a model for CF3 reorientation. As such, these experiments provide much more information than when only one spin species (usually (1)H) is present. In Sec. IV, which can be read immediately after the Introduction without reading the rest of the paper, we compare the barrier to CH3 and CF3 reorientation in seven organic solids and separate this barrier into intramolecular and intermolecular components.

Elasto-dipolar magnons—a new class of nonexchange spin-wave excitations

Interference of phonon and magnetic dipolar spin-spin interaction mechanisms in a finite magnet can result in a previously unexplored class of nonexchange spin waves.

Controlling the dipole-dipole interaction using NMR composite rf pulses.

New composite rf pulses are proposed during which the average dipole-dipole interactions within a spin ensemble are controlled, while a global rotation is achieved. The method used to tailor the pulses is based on the average Hamiltonian theory and relies on the geometrical properties of the spin-spin dipolar interaction. I describe several such composite pulses and analyze quantitatively the improvement brought on the control of the NMR dynamics. Numerical simulations show that the magic sandwich pulse sequence, during which the average dipolar field is effectively reversed, is plagued by defects originating from the finite initial and final π/2 rf pulses. A numerical test based on a classical description of nuclear magnetic resonance is used to check that, when these pulses are replaced by magic composite pulses, the efficiency of the magic sandwich is improved.

Electron Spin Polarization Transfer from Photogenerated Spin-Correlated Radical Pairs to a Stable Radical Observer Spin

A series of donor-chromophore-acceptor-stable radical (D-C-A-R(•)) molecules having well-defined molecular structures were synthesized to study the factors affecting electron spin polarization transfer from the photogenerated D(+•)-C-A(-•) spin-correlated radical pair (RP) to the stable radical R(•). Theory suggests that the magnitude of this transfer depends on the spin-spin exchange interaction (2JDA) of D(+•)-C-A(-•). Yet, the generality of this prediction has never been demonstrated. In the D-C-A-R(•) molecules described herein, D is 4-methoxyaniline (MeOAn), 2,3-dihydro-1,4-benzodioxin-6-amine (DioxAn), or benzobisdioxole aniline (BDXAn), C is 4-aminonaphthalene-1,8-dicarboximide, and A is naphthalene-1,8:4,5-bis(dicarboximide) (1A,B-3A,B) or pyromellitimide (4A,B-6A,B). The terminal imide of the acceptors is functionalized with either a hydrocarbon (1A-6A) or a 2,2,6,6-tetramethyl-1-piperidinyloxyl radical (R(•)) (1B-6B). Photoexcitation of C with 416-nm laser pulses results in two-step charge separation to yield D(+•)-C-A(-•)-(R(•)). Time-resolved electron paramagnetic resonance (TREPR) spectroscopy using continuous-wave (CW) microwaves at both 295 and 85 K and pulsed microwaves at 85 K (electron spin-echo detection) was used to probe the initial formation of the spin-polarized RP and the subsequent polarization of the attached R(•) radical. The TREPR spectra show that |2JDA| for D(+•)-C-A(-•) decreases in the order MeOAn(+•) > DioxAn(+•) > BDXAn(+•) as a result of their spin density distributions, whereas the spin-spin dipolar interaction (dDA) remains nearly constant. Given this systematic variation in |2JDA|, electron spin-echo-detected EPR spectra of 1B-6B at 85 K show that the magnitude of the spin polarization transferred from the RP to R(•) depends on |2JDA|.

Structure and Dynamics of Photogenerated Triplet Radical Ion Pairs in DNA Hairpin Conjugates with Anthraquinone End Caps

A series of DNA hairpins (AqGn) possessing a tethered anthraquinone (Aq) end-capping group were synthesized in which the distance between the Aq and a guanine-cytosine (G-C) base pair was systematically varied by changing the number (n - 1) of adenine-thymine (A-T) base pairs between them. The photophysics and photochemistry of these hairpins were investigated using nanosecond transient absorption and time-resolved electron paramagnetic resonance (TREPR) spectroscopy. Upon photoexcitation, (1*)Aq undergoes rapid intersystem crossing to yield (3*)Aq, which is capable of oxidizing purine nucleobases resulting in the formation of (3)(Aq(-•)Gn(+•)). All (3)(Aq(-•)Gn(+•)) radical ion pairs exhibit asymmetric TREPR spectra with an electron spin polarization phase pattern of absorption and enhanced emission (A/E) due to their different triplet spin sublevel populations, which are derived from the corresponding non-Boltzmann spin sublevel populations of the (3*)Aq precursor. The TREPR spectra of the (3)(Aq(-•)Gn(+•)) radical ion pairs depend strongly on their spin-spin dipolar interaction and weakly on their spin-spin exchange coupling. The anisotropy of (3)(Aq(-•)Gn(+•)) makes it possible to determine that the π systems of Aq(-•) and G(+•) within the radical ion pair are parallel to one another. Charge recombination of the long-lived (3)(Aq(-•)Gn(+•)) radical ion pair displays an unusual bimodal distance dependence that results from a change in the rate-determining step for charge recombination from radical pair intersystem crossing for n < 4 to coherent superexchange for n > 4.

High-Resolution Myosin Structure from DEER Using a Bifunctional Spin Label

We are using site-directed spin-labeling (SDSL) and dipolar electron-electron resonance (DEER) to study the structural dynamics of proteins involved in muscle function. Muscle proteins are ideal systems for DEER applications, since these proteins form large dynamic assemblies that are inaccessible to crystallography and NMR. DEER is a pulsed ELDOR technique that detects the spin-spin dipolar interaction as a decay and modulation of a spin echo signal. While the CW EPR spectrum is sensitive only to distances on the order of 1 to 2 nm, DEER is sensitive from 1.5 to 5 nm and more. DEER is sensitive to the width of the distance distribution and can resolve multiple structural populations simultaneously. However, a limitation of DEER is the use of spin probes with flexible linkers, which adds uncertainty to the locations of protein backbone atoms. A bifunctional spin label (BSL), which attaches at position (i, i+4) of a helix, was used to measure the distance between two di-Cys pairs. BSL is rigidly coupled to the protein backbone and is a breakthrough for high resolution measurement of orientation, dynamics, and distance. These distance measurements were compared to conventional labeling of cysteine residues with MSL/MSL pairs.

Cold collisions of an open-shell S-state atom with a 2Π molecule: N(4S) colliding with OH in a magnetic field

We present quantum-theoretical studies of collisions between an open-shell S-state atom and a (2)Π-state molecule in the presence of a magnetic field. We analyze the collisional Hamiltonian and discuss possible mechanisms for inelastic collisions in such systems. The theory is applied to the collisions of the nitrogen atom ((4)S) with the OH molecule, with both collision partners initially in fully spin-stretched (magnetically trappable) states, assuming that the interaction takes place exclusively on the two high-spin (quintet) potential energy surfaces. The surfaces for the quintet states are obtained from spin-unrestricted coupled-cluster calculations with single, double, and noniterative triple excitations. We find substantial inelasticity, arising from strong couplings due to the anisotropy of the interaction potential and the anisotropic spin-spin dipolar interaction. The mechanism involving the dipolar interaction dominates for small magnetic field strengths and ultralow collision energies, while the mechanism involving the potential anisotropy prevails when the field strength is larger (above 100 G) or the collision energy is higher (above 1 mK). The numerical results suggest that sympathetic cooling of magnetically trapped OH by collisions with ultracold N atoms will not be successful at higher temperatures.