The Excited Triplet State of Azoalkanes: Electron Spin Polarization and Magnetic Field Effects During Triplet-Sensitized Photolysis of trans-Azocumene in Solution

The triplet-sensitized photodecomposition of azocumene into nitrogen and cumyl radicals is investigated by time-resolved electron paramagnetic resonance and absorption spectroscopy. The radicals are found to be created spin polarized with a yield depending on the strength of the applied magnetic field. The phenomenon arises because in triplet azocumene, the decay into radicals competes with a fast triplet-sublevel selective intersystem crossing back to the azocumene ground state. The size of the initial spin polarization of the radicals and the magnetic field effect on their yield are determined in solvents of different viscosities. Data analysis yields rate constants for the intersystem crossing and the cleavage reaction of triplet azocumene as well as its zero-field splitting D _ZFS. At room temperature in nonpolar solvents, the most probable values are: k _x ?=?k _y ?=?1.2?×?10¹¹?s^?? and k _z ?=?1.9?×?10¹⁰?s^?? for the intersystem crossing from the energetically lower and upper triplet substates, respectively, k _p ?=?1.6?×?10⁹?s^?? for the cleavage reaction and for the zero-field splitting D _ZFS?=???.4?×?10^10?s^?? (0.18?cm^??).     

Electron Spin Resonance Study on the Photoinduced Electron Transfer in Chlorophyll a in Reconstituted Lipid Bilayer Vesicles

Abstract  

The photoinduced electron transfer from chlorophyll a through the interface of positively charged dioctadecyltrimethylammonium chloride (DODAC), neutral dipalmitoylphosphatidylcholine (DPPC) and negatively charged dihexadecylphosphate (DHP) headgroup of the lipid bilayers was studied. The photoinduced radicals were identified by electron spin resonance (ESR) and radical yields of chlorophyll a were determined by double integration of the ESR spectra. The formation of vesicles was identified indirectly by measuring change of the λ _max value of optical absorption spectrophotometer from diethyl ether solution to vesicle solutions, and observed directly with scanning and transmission electron microscopic images. The interaction distance between chlorophyll a and interface water (D₂O) determined by deuterium modulation depth with electron spin echo modulation (ESEM) showed a decreasing order DODAC > DPPC > DHP. The interface charge of each vesicle was determined with zeta potential measurement. The interface charge of the lipid bilayers affected the radical yields of chlorophyll a more critically than the interaction distance between chlorophyll a and interface water.     

乙腈-水和乙二醇-水均相溶液中光诱导杜醌激发三重态与色氨酸、酪氨酸的氢原子转移反应

本文用激光闪光光解技术研究了光诱导生物醌杜醌激发三重态(³DQ^*)和色氨酸(Trp)与酪氨酸(Tyr)在乙腈-水(MeCN-H₂O)及乙二醇-水(EG-H₂O)均相溶液中的光化学反应,分析了反应的机理,并基于Stern-Volmer方法测量了反应速率常数. 光解DQ体系可以生成³DQ^*,³DQ^*与Trp、Tyr发生的氢原子转移反应占主导地位. 对于DQ/Trp/MeCN-H₂O和DQ/Trp/EG-H₂O溶液,³DQ^*与Trp反应生成杜醌中性自由基DQH^·、以碳为中心的色氨酸中性自由基Trp^·/NH和以氮为中心的色氨酸中性自由基Trp/N^·. 对于DQ/Tyr/MeCN-H₂O和DQ/Tyr/EG-H₂O溶液,³DQ^*与Tyr反应生成DQH^·和酪氨酸中性自由基Tyr/O^·. ³DQ^*与Trp、Tyr的氢原子转移反应速率常数都在10⁹ L·mol^-1·s^-1量级,反应近似受扩散控制. MeCN/H₂O均相溶液中³DQ^*与Trp、Tyr的反应速率常数要明显高于EG/H₂O均相溶液中的反应速率常数,这与Stokes-Einstein方程定性一致.     

Effect of Quasi-Fermi Level on the Degree of Electron Spin Polarization in GaAs

With spin-polarized-dependent band gap renormahzation effect taken into account,the energy-dependent evolution of electron spin polarization in GaAs is calculated at room temperature and at a low temperature of 10 K.We consider the exciting light with right-handed circular polarization,and the calculation results show that the degree of electron spin polarization is dependent strongly on the quasi-Fermi levels of |1/2 and |-1/2 spin conduction bands.At room temperature,the degree of electron spin polarization decreases sharply from 1 near the bottom of the conduction band,and then increases to a stable value above the quasi-Fermi level of the |—1/2 band.The greater the quasi-Fermi level is,the higher the degree of electron spin polarization with excessive energy above the quasi-Fermi level of the |-1/2 band can be achieved.At low temperature,the degree of electron spin polarization decreases from 1 sharply near the bottom of the conduction band,and then increases with the excessive energy,and in particular,up to a maximum of 1 above the quasi-Fermi level of the |1/2 band.     

Influence of C60 Aggregation on Pseudorotation in the Excited Triplet State Probed by Multifrequency Time-Resolved EPR

The influence of C₆₀ aggregation on time-resolved (TR) electron paramagnetic resonance (EPR) of C₆₀ in the excited triplet state was investigated by multifrequency EPR techniques. Temperature-independent X-band (9.7 GHz) TR-EPR spectra were observed in a fresh toluene solution, while temperature-dependent ones were reported in literatures. The experimental spectra in this study indicated that the pseudorotation of pristine C₆₀ in frozen toluene solution is not frozen out even at lower temperatures. Careful investigations of TR-EPR and its decay kinetics demonstrated that the pseudorotation can be affected by C₆₀ aggregation. A comparison between X- and W-band (94.9 GHz) results indicated that the aggregation can be accelerated by a capillary effect. Three decay constants were extracted from the analysis of the decay kinetics. The fastest component was ascribed to the pseudorotation, which was independent of temperature in the range of 10–40 K. The temperature dependences of the decay kinetics showed that the pseudorotation is not affected by C₆₀ aggregation at higher temperatures.     

Electron Spin Echo of Photoinduced Spin-Correlated Polaron Pairs in P3HT:PCBM Composite

A variation of the electron spin echo (ESE) signal caused by laser pulse in a blend of [6,6]-phenyl C₆₁ butyric acid methyl ester and poly(3-hexylthiophene) (P3HT:PCBM) was detected. This variation was attributed to light-generated paramagnetic species in P3HT:PCBM blend, with non-equilibrium spin polarization. The echo-detected electron paramagnetic resonance (EPR) spectrum of these species closely resembles the time-resolved EPR spectrum of spin-correlated polaron pair PCBM^?/P3HT⁺ (Behrends et al. in Phys. Rev. B 85:125206, 2012) and was assigned to this pair. The characteristic times for polarization and coherence decay (9 ± 1 and 1.0 ± 0.2 μs, respectively) were measured for the PCBM^?/P3HT⁺ pair at 77 K. These times are long enough, which shows the possibility of the application of the ESE technique for studying spin evolution of light-generated charge transfer intermediates in composites of fullerenes and conductive polymers.     

Electron Capture Process in Collisions of Proton with Excited State of Helium

Total and star,selective cross sections for single electron capture （SEC） from the n = 2 excited state of helium colliding by protons are calculated in the energy range of 1.0-100.0 ke V/u by using the two-center atomic orbital close-coupling method. The interaction of the active electron with helium ion is represented by a model potential. Total SEC cross sections show a monotonic decreasing trend with increasing collision energy, and display a different behavior compared with the case from the ground state of helium. It is also found that the dominant reaction channel is captured to the H（2p） state up to 40 keV//u, and then the capture to the H（1s） or H（2s） state becomes more pronounced. Moreover, the alignment dependence on the initial states is obtained for the electron capture from He（2p0） and He （2p1）.     

维生素C对菲醌三重激发态的淬灭机理及动力学研究

用时间分辨电子自旋共振技术研究了乙二醇(EG)均相溶液和反胶束溶液中抗氧化剂维生素C(VC)对菲醌(PAQ)分子激发三重态³PAQ*的淬灭反应．利用反胶束模拟生物细胞和组织的生理环境．光解PAQ/EG-H₂O均相溶液,³PAQ*与溶剂分子EG之间发生氢转移反应．当体系中加入VC后,³PAQ*不仅从EG上夺氢,还从VC上夺氢,VC对³PAQ*的淬灭速率常数为1.409×10⁸ L/(mol·s), 反应受扩散控制． 在CTAB/EG-H₂O和AOT/EG-H₂O反胶束溶液中,³PAQ*和VC之间的夺氢反应发生在反胶束的水/油界面附近,³PAQ*扩散到油/水界面的过程降低了反应的速率．对于TX-100/EG-H₂O反胶束溶液, 由于PAQ增溶于亲水的聚氧乙烯链中,VC对³PAQ*的淬灭速率常数比CTAB/EG-H₂O和AOT/EG-H₂O反胶束中的都大,甚至比EG-H₂O均相溶液中的也略大．很强的VC负离子自由基As^-的CIDEP信号来源于³PAQ*与VC之间发生抽氢反应过程中的三重态机理自旋极化转移     

The Effect of a Magnetic Field on Photoinduced Electron Transfer in Solutions of Chlorophyll and Porphyrins

It is found that, with the action of photoexcitation and a variable magnetic field on halide-containing porphyrin solutions, a differential absorption is observed, whose spectra conform to the absorption spectra of cation radicals of pigments. It is shown that the effect increases linearly with an increase in the strength of a supplementary magnetic field (H) up to saturation (H _max 200 G). The scheme of the photophysical and photochemical deactivation of the energy of electronic excitation for chlorophyll-like pigments in the presence of CCl₄ is analyzed with allowance for the effect of the magnetic field on the intercombination conversion in an ion–radical pair. It is shown that solvate-separated ion radicals of the pigments in halide-containing solutions can be formed from the singlet state of tetrapyrrole molecules.     

Cl+HD反应产物的极化与态分布

利用准经典轨线理论 ,在BW 2和G3两个势能面上 ,研究了Cl +HD反应的动力学 .计算结果表明 ,产物的转动取向对势能面及反应体系的质量因子非常敏感 .在BW 2势能面上 ,计算的两个产物的转动取向强于在G3势能面上计算的结果 ,而无论是在BW 2势能面上还是在G3势能面上 ,DCl产物的取向都强于HCl产物的取向 .计算结果还表明 ,在不同的势能面上反应物的转动激发对反应的影响有着显著的不同 .在BW 2势能面上 ,反应物的初始转动激发有利于Cl+HD反应的进行 ;而在G3势能面上 ,反应物的初始转动激发消弱了反应的反应性     

轨道诱导Peierls相变材料MgTi_2O_4的电子自旋共振研究

用变温电子自旋共振手段(Electron Spin Resonance,ESR),对轨道诱导Peierls相变MgTi_2O_4体系进行了研究.研究发现,轨道诱导Peierls相变所伴随的自旋二聚相变对ESR谱产生了影响.在相变温度以上,MgTi_2O_4的磁性为顺磁行为.而在相变温度以下,ESR谱显示MgTi_2O_4的磁性偏离了顺磁行为.对ESR谱线的参数拟合结果显示,MgTi_2O_4在发生轨道诱导Peierls相变时,自旋耦合作用逐渐增强.这说明:自旋耦合作用的增强很有可能是导致相变的一个重要的因素.     

轨道诱导Peierls相变材料MgTi2O4的电子自旋共振研究

用变温电子自旋共振手段,对轨道诱导Peierls相变MgTi2O4体系进行了研究。研究发现,轨道诱导Peierls相变所伴随的自旋二聚相变对ESR谱产生了影响。在相变温度以上,MgTi2O4的磁性为顺磁行为。而在相变温度以下,ESR谱显示MgTi2O4的磁性偏离了顺磁行为。对ESR谱线的参数拟合结果显示,MgTi2O4在发生轨道诱导Peierls相变时,自旋耦合作用逐渐增强。这说明:自旋耦合作用的增强很有可能是导致相变的一个重要的因素。     

PSⅡ中蛋白二级结构中β聚合效应的红外光谱研究

利用Fourier变换红外光谱（FTIR）方法研究了光系统Ⅱ（PSⅡ）膜颗粒中蛋白二级结构在高温条件下的β聚合效应。具有生物活性和高温蛋白的β聚合样品的红外光谱测量温度均是室温，它们的酰胺Ⅰ吸收带被用来对两种样品的特性进行定量的分析。光谱的分析方法采用了直接Lorentz线型拟合，光谱结果表明光系统Ⅱ二级结构在400℃下发生热变性后，其红外光谱将发生很强的不可逆的变化。但其红外光谱与活性PSⅡ蛋白一样仍可用3个Lorentz线型拟合，显示了FTIR红外光谱方法在研究蛋白热变性方面的优越性。     

On the Origin of the Lowest Excited Singlet State in Retinyl Acetate

Abstract

Employing the techniques of a circular dichroism (CD) and a fluorescence polarization (FP), the long-wavelength forbidden ¹A^?- _g → ¹A^? _g transition in the absorption spectrum of retinyl acetate at 293K has been found. The FP degree of retinyl acetate in cyclohexanol decreases from 0.28 at 330 nm (the area of a strongly allowed ¹B?_u → ¹A^? _g transition) to 0.21 at 360 nm (the area of forbidden ¹A^?- _g → ¹A^? _g transition).     

Effect of Quantum Point Contact Measurement on Electron Spin State in Quantum Dots

We study the time evolution of two electron spin states in a double quantum-dot system, which includes a nearby quantum point contact （QPC） as a measurement device. We find that the QPC measurement induced decoherence is in the microsecond timescale. We also find that the enhanced QPC measurement will trap the system in its initial spin states, which is consistent with the quantum Zeno effect.     

Orientation Information from the Dipolar Interaction Between a Complex in the Excited Quartet State and a Doublet Spin Label

An algorithm is proposed for deriving the position of a stable radical relative to a photoexcited quartet state from the electron spin–spin interactions measured by double resonance methods. Intersystem crossing generates multiplet polarization in the quartet state and microwave excitation of the ±3/2 ? ±1/2 transitions converts the multiplet polarization into net polarization of the ±1/2 levels. The dependence of the electron spin echo envelope modulation (ESEEM) of the +1/2 ? ?1/2 transition on the field/frequency of the stimulation pulse is demonstrated. The algorithm is tested by comparing the predicted ESEEM patterns to those from explicit numerical calculations of the spin evolution (so-called numerical experiments), which act as a model for experiment results. The comparison demonstrates that within the point-dipole approximation it is feasible to obtain not only the distance between the two paramagnetic centers but also the orientation of the distance vector relative to the principal axes of the quartet state.     

On the Ground State of Spin Systems with Orbital Degeneracy

In order to understand the properties of the spin system with orbital degeneracy,we first study the ground state of the SU(4) spin-orbital model on a square lattice.The mean-field results suggest that for a small Hund‘s interaction,the flavor liquid state is stable against the solid state,but with sufficient deviation from the SU(4) limit the long-range order may be attained in 2D system.Furthermore,we employ a variational approach to calculate the phase diagram of the ground state and the temperature-dependent susceptibility by taking into account the Hund‘s interaction and the anisotropy in orbital wavefunctions.Finally,the implications for the experimental observations on the material,LiNiO2,are discussed.