Low field RYDMR: effects of orthogonal static and oscillating magnetic fields on radical recombination reactions

Reactions involving spin correlated radical pairs as intermediates are known to be sensitive to applied static and/or oscillating magnetic fields. In the reaction yield detected magnetic resonance (RYDMR) technique, an electromagnetic field in resonance with the electron Zeeman splitting produced by a strong static field is used to perturb the singlet ? triplet interconversion of the radical pair and so to affect the yield of geminate recombination. New experiments are described in which weak radiofrequency fields (? 300μT) in the frequency range 1–80 MHz are applied to radical ion pairs derived from pyrene and 1,3-dicyanobenzene, in the presence of a weak (? 3.0 mT) static magnetic field. Such experiments test the viability of RYDMR in low fields, provide insight into the crossover region between the zero-field and high field cases, and may give information on the distribution of radical pair lifetimes.     

Effect of variation of dielectric constant on the magnetic field modulation of exciplex luminescence

The effect of variation of dielectric constant on the relative magnetic field effect in singlet luminescence has been studied using a typical exciplex system at a saturating field. The study indicates strong specificity in the perturbation of the magnetic field effect by alcoholic solvents. In contrast to alcohols where relative singlet magnetic field effect is of the order of 2% only, the magnetic field effect in non-alcoholic medium reaches as high as 9%. Moreover, dielectric constant variation in alcohols yields curves which are distinctly different from those in non-alcoholic media. It turns out that this dependence of magnetic field effect on dielectric constant is similar in all non-alcoholic solvent mixtures. An analytical study based on Hong and Noolandi’s solution of Smoluchowski equation has been made. Derived expressions can interpret experimental curves reasonably well.     

Control of the sign of exchange interactions in solvent-separated radical ion pairs

The chemically induced dynamic electron polarization spectra generated by the laser photolysis of several donor-acceptor systems have been studied to verify the solvent effects on the exchange interaction in solvent-separated radical ion pairs. It has been shown that the sign of the exchange interaction depends on the polarity of solvents. The individual reorganization energies have been determined for several solvent-separated radical ion pair systems.     

Reaction-yield-detected magnetic resonance in the intra-and intermolecular electron transfer reactions

The spin dynamics of the intermediate radical ion pairs formed in the intra-and intermolecular electron transfer reactions between N,N-dimethylaniline and phenanthrene is studied by employing the polymethylene-linked and nonlinked systems. Reaction-yield-detected magnetic resonance (RYDMR) experiments are performed by monitoring the exciplex fluorescence. From the theoretical consideration of the data, we conclude that the lifetime of the radical ion pair in the linked system is shorter than that in the nonlinked system. This tendency is opposite to what is generally observed in linked and nonlinked neutral biradical.     

Observation and reaction control of a singlet born radical pair formed photochemically in an SDS micelle by pulsed microwave irradiation

The photochemical reaction of tetraphenylhydrazine in an SDS micellar solution is studied using a transient absorption detected magnetic resonance (ADMR) method. This system is photo-dissociated via the singlet excited state and forms a transient radical pair. Strong microwave irradiation of this system under an × band EPR magnetic field provides an ADMR spectrum of the singlet born radical pair as the optical absorbance change of the diphenylaminyl radical. The employment of a short duration microwave pulse that efficiently flips the electron spin quantum (Δm _s = 1) controls the reaction of the radical pair, and the reaction rate constant of this system is determined. Furthermore, changing the microwave duration shows the quantum beat of this system induced by the electromagnetic field. This beat signal carries both a single beat that corresponds to the Rabi frequency and a double-frequency beat that is due to simultaneous two-spin controlling.     

Studies on coherent and incoherent spin dynamics that control the magnetic field effect on photogenerated radical pairs

Since 1970s, magnetic field effects (MFEs) on photogenerated radical pairs have been the centre of focus in the field of spin chemistry. The MFE attributes to quantum mechanical interconversion between the singlet and triplet radical pair states and subsequent spin-selective recombination reactions. In this New View article, the author picks up two hot topics studied during the last two decades, which are (i) so-called low field effect (LFE) and (ii) 2J-resonance MFE on fixed distance donor–acceptor linked molecules. In both of the topics, quantum mechanical explanations are given referring to recent reports, and some novel calculations have been carried out for bridging theoretical and experimental data for long-lived radical pairs. For the first topic, time domain calculations of coherent state mixing have been carried out for elucidation of hyperfine (HF) structure dependence of the LFE. For the second topic, Monte Carlo simulations of the torsional motion of polyaromatic linker unit have been carried out for the demonstration of fast decoherence in such rigid molecules. From these considerations, future possibilities of MFE studies on photo-functional materials and biomolecules have been indicated.     

Magnetic field effects on the pyrene—dicyanobenzene system: determination of electron self-exchange rates by MARY spectroscopy

An experimental determination has been made of electron self-exchange rates between the radical anions of 1,2-, 1,3- and 1,4-dicyanobenzene (DCB) and the respective neutral molecules applying steady-state field-modulated MARY (magnetic field effect on reaction yield) spectroscopy. For the first time this has been achieved successfully for compounds whose self-exchange rate constants can be obtained independently by alternative methods such as EPR linebroadening. In this study, pyrene was used as an electron donor to generate the spin-correlated radical ion pair (pyrene·⁺ DCB·^?) essential for MARY spectroscopy. The radical ion pair is in equilibrium with an exciplex whose magnetic field affected fluorescence was recorded as a function of the magnetic field to yield the MARY spectrum. Due to lifetime uncertainty energy broadening of spin levels caused by electron self-exchange, the characteristic B _1/2 value increases with the concentration of DCB in the sample. The rate constant of self-exchange was obtained from the slope of the linear part in the plot of B_1/2 versus DCB concentration. The values range between 6 x 10⁸ M^?1 s^?1 and 1.4 x 10¹⁰ M^?1 s^?1, depending on the DCB isomer and solvent. Comparison with literature data from EPR linebroadening measurements shows good agreement.     

Multiplet-to-net CIDEP conversion by MW-pulses with adiabatically ramped amplitude

ABSTRACT

A method is proposed to manipulate electron spin order of spin-correlated radical pairs. As radical pairs are often born in a well-defined spin state, e.g. in the singlet state, they acquire Chemically Induced Dynamic Electron Polarisation (CIDEP). In the case of singlet-state preparation CIDEP is of the multiplet (or anti-phase) type resulting in reduction of EPR (electron paramagnetic resonance) signals due to overlap of absorptive and emissive lines in the spectrum. Here we propose to convert the singlet spin order into net magnetisation of the radical pair by applying a microwave field, with its amplitude slowly (adiabatically) reduced to zero. We demonstrate that by properly choosing the microwave frequency one can completely convert the singlet order into net polarisation of the radical pair with significant enhancement of the signal as compared to multiplet CIDEP. Calculations show that the technique is operative for both weakly coupled and strongly coupled spin pairs. Potential applications of the method are discussed.     

Paramagnetic relaxation of radical cations in alkane solutions as measured by time-resolved magnetic field effects

Spin-lattice relaxation times of radical cations were measured by the decay of the time-resolved magnetic field effect in the recombination fluorescence of radical ion pairs in liquid hydrocarbons at high concentrations of solvent holes acceptor. The dependences of spin-lattice relaxation time on the magnetic field strength and solvent viscosity were studied. The results could not be explained in terms of the model of ion-molecular charge transfer involving monomeric or dimeric radical cations. The paramagnetic relaxation observed in a weak magnetic field is attributed to internal reorganizations of aggregates that originate from radical cations at high acceptor concentration.     

A Low-Field Magnetically Affected Reaction Yield (MARY) Spectrometer with Spectral Fluorescence Resolution

A novel spectrometer for low-field studies in magnetically affected reaction yield (MARY) spectroscopy with fluorescence detection is described. The spectrometer is based on a yoke-free magnetic system containing no ferromagnetic elements, uses X-ray or optical excitation, and includes a monochromator to analyze the spectral composition of luminescence. Using the new setup, the effect of transversal residual magnetic field on zero field MARY line is illustrated, formation of exciplexes under X-irradiation in a naphthalene/N,N-dimethylaniline solution in alkane is demonstrated, a magnetic field effect on the emission spectrum is shown in field-cycling mode, and modulated MARY spectra in the exciplex and the intrinsic luminophor bands are compared to show that magnetic field sensitivity here is provided at the stage of the recombining radical ion pair, while exciplex formation only transforms the luminescence properties.     

Solvent effects on the intrinsic enhancement factors of the triplet exciplex generated by photoinduced electron transfer reaction between eosin Y and duroquinone

The spin dynamics of the duroquinone anion radical (DQ^?-) generated by photoinduced electron transfer reactions from triplet eosin Y (³EY^2-) to DQ have been studied by using transient absorption and pulsed EPR spectroscopy. Unusual net-absorptive electron spin polarization plus net-emissive polarization were observed, suggesting the production of the triplet exciplex or contact radical pair as the reaction intermediate. The kinetic parameters and intrinsic enhancement factors of the electron spin polarization were determined in various alcoholic solvents. The net-absorptive electron spin polarization was also observed in ethanol-water mixed solvents. The solvent effects on the radical yield are analysed on the basis of a stochastic Liouville equation established for the magnetic field effects on the radical yield. The zero-field splitting constants of the triplet exciplex are estimated from the solvent viscosity dependence of the enhancement factors due to spin-orbit coupling induced depopulation of the reaction intermediate.     

Singlet-triplet splitting of geminate electron-hole pairs in conjugated polymers

The singlet-triplet splitting of geminate polaron pairs in a ladder-type conjugated polymer has been studied by the thermally stimulated luminescence technique. The energy gap separating the singlet and triplet states of the geminate pairs is measured to be in the range of 3-6 meV, depending on the polymer morphology. The results of correlated quantum-chemical calculations on a long ladder-type oligomer are fully consistent with the observed values of the geminate polaron pair singlet-triplet gap. Such low splitting values have important implications for the spin-dependent exciton formation in conjugated polymers.     

氢负离子在磁场和电介质表面附近光剥离的研究

利用闭合轨道理论, 研究了变化的磁场和不同电介质表面对氢负离子光剥离截面的影响, 并推导出了该体系下的光剥离截面公式. 结果发现, 氢负离子的光剥离截面不仅与磁场的强度有关, 而且还与电介质常数有关. 当氢负离子到电介质表面的距离和电介质常数一定时, 体系的光剥离截面中的振荡随磁场的变化而明显变化. 随着磁场强度的 增大, 体系的闭合轨道数目增多, 光剥离截面的振荡越来越复杂. 当氢负离子到电介质表面的距离和磁场强度一定时, 电介质常数的变化对光剥离截面的影响也很重要, 随着电介质常数的增大, 体系的闭合轨道数目增多, 光剥离截面的振荡也变得越来越复杂. 因此, 可以通过改变磁场强度和电解质常数来调整负离子的光剥离截面. 此结果 对于研究负离子体系在表面附近和外场中的光剥离问题具有一定的参考价值.     

Radio frequency magnetic field effects on electron-hole recombination

We present measurements of the spectrum (1--80 MHz) of the effect of a weak (approximately 500 microT) radio frequency magnetic field on the electron-hole recombination of radical ion pairs in solution. Distinct spectra are observed for the pyrene anion/dimethylaniline cation radical pair in which one or both of the radicals are perdeuterated. The radical pair mechanism is developed theoretically and shown to account satisfactorily for both the magnetic field effect and the associated magnetic isotope effect.     

GaAs电介质表面对剥离电子通量分布影响的数值研究

利用半经典开轨道理论,研究了GaAs电介质表面对氢负离子在磁场中的光剥离干涉图样的作用,推导并计算了本体系下的光剥离电子流通量,主要研究GaAs电介质表面到离子的距离不同对电子通量的影响。结果表明,电介质表面到离子的距离可以改变电子通量分布中的振荡结构,影响探测平面上形成的干涉图样的分布。因此,可以通过改变电介质表面到离子的距离来调控剥离电子的通量和干涉图样分布。     

Large magnetic field effect on back electron transfer from uncharged radical to its cationic partner in anionic micelle

The magnetic field effect (MFE) on the radical pair (RP) generated by photoexcitation of the acetyl derivative of phenyl pyrylium ion (APP⁺) in the presence of biphenyl, an electron donor, has been investigated. The escape yield at 3.5 T is more than ten times the zero-field value. The MFE reaches near-saturation twice, once at fields of the order of 10mT and again at about 3.5 T. The low-field variation of the MFE conforms to the pattern expected for the isotropic HFC mechanism, and the high-field variation to that expected for the relaxation mechanism. In this particular system two types of radical pair are generated, one by electron transfer from the donor to the acceptor and another by H-abstraction from the micelle. The MFEs on the two types of ³RP have been compared.     

Investigations on the Photoreactions of Phenothiazine and Phenoxazine in Presence of 9-cyanoanthracene by Using Steady State and Time Resolved Spectroscopic Techniques

By using electrochemical, steady state and time resolved (fluorescence lifetime and transient absorption) spectroscopic techniques, detailed investigations were made to reveal the mechanisms of charge separation or forward electron transfer reactions within the electron donor phenothiazine (PTZH) or phenoxazine (PXZH) and well known electron acceptor 9-cyanoanthracene (CNA). The transient absorption spectra suggest that the charge separated species formed in the excited singlet state resulted from intermolecular photoinduced electron transfer reactions within the donor PTZH (or PXZH) and CNA acceptor relaxes to the corresponding triplet state. Though alternative mechanisms of via formations of contact neutral radical by H-transfer reaction have been proposed but the observed results obtained from the time resolved measurements indicate that the regeneration of ground state reactants is primarily responsible due to direct recombination of triplet contact ion-pair (CIP) or solvent-separated ion-pair (SSIP).     

Photodetachment microscopy of H~- in the magnetic field near different dielectric surfaces

We study the photo-detachment interference patterns of a hydrogen negative ion in the magnetic field near different dielectric surfaces with a semi-classical open orbit theory.We give a clear physical picture describing the photo-detachment of H-in this case.The electron flux distributions are calculated at various dielectric surfaces with unchanged magnetic field strength.It is found that the electron flux distributions of H-are very different in a magnetic field near different dielectric surfaces,namely the dielectric surface has a great influence on the photo-detachment interference pattern of the negative ion.Therefore,the interference pattern in the detached-electron flux distribution can be controlled by changing the dielectric constant.We hope that our studies may guide the future experimental research in photo-detachment microscopy.     

Multifrequency time-resolved EPR (9.5GHz and 95GHz) on covalently linked porphyrin-quinone model systems for photosynthetic electron transfer: effect of molecular dynamics on electron spin polarization

Covalently linked porphyrin–quinone model systems for photosynthetic electron transfer were examined by using time-resolved electron paramagnetic resonance (TREPR) at intermediate magnetic field and microwave frequency (0.34T/9.5GHz, X-band) and high field and frequency (3.4T/95GHz, W-band). The paramagnetic transients studied were the light-induced spin-correlated radical pair states of the donor–acceptor complex in polar solvents below the melting point and in the soft glass phase of a liquid crystal. It is shown that the systems form strongly exchange-coupled radical pairs, whose TREPR lineshapes are determined mainly by fast electron recombination together with both spin–lattice relaxation and modulation of the exchange interaction. Below the melting point the spin–lattice relaxation rate naturally slows down, but that of the spin on the quinone site is still of the order of 10⁶ s^-1. Most probably this is due to contributions from spin–rotation interaction, and dependent on the molecular orientation with respect to the magnetic field. This relaxation anisotropy is related to anisotropic motion of the quinone site in the solvent cage. The results allow conclusions to be drawn concerning the molecular dynamics and flexibility of the systems. To yield long-lived radical pair states that would mimic photosynthetic electron transfer, the two mechanisms described, modulation of exchange and spin–rotation interactions, have to be suppressed by reducing the molecular flexibility of the complex.     

强脉冲磁场冲击处理对铝基复合材料塑性的影响机制

铝基复合材料在加入颗粒相之后, 延伸率和塑性变形能力明显降低. 为改善其塑性变形能力, 通过对比强脉冲磁场冲击处理前后试样内部组织和残余应力的变化特征, 研究了磁致塑性效应对铝基复合材料塑性变形能力的影响机理. 结果表明: 当磁感应强度从2 T变化到4 T时, 铝基复合材料中位错密度显著增加, 4 T时的位错密度是未加磁场时的3.1倍; 3 T, 30个脉冲处理后的复合材料中残余应力值从未加磁场时的41 MPa减小为-1 MPa. 从原子尺度来看, 强磁场导致了磁致塑性效应, 从而引起了位错的运动, 并促进了位错的退钉扎和可移动位错数量的增加; 从材料内部整体结构变化来看, 磁场加速了材料内应力的释放速率, 降低了材料内部的残余应力, 从而改善了铝基复合材料的塑性变形能力.