三重态分子/稳定自由基体系超精细相关CIDEP的理论计算

光激发三重态分子/氮氧自由基的乙二醇溶液得到E+E/A极化的CIDEP谱,以光激发三重态与二重态自由基相互作用模型,考虑自由基的超精细相互作用,利用二阶微扰理论及相互作用表象下的密度矩阵,理论上计算了此类体系的CIDEP.     

光解杜醌/氢给体均相体系的CIDEP研究

以杜醌为光敏剂,用高时间分辨电子自旋共振 (TRESR)波谱仪研究了杜醌/乙二醇体系、杜醌/氮氧自由基/乙二醇体系的化学诱导动态电子自旋极化(CIDEP).实验表明,紫外激光照射下,在杜醌/乙二醇溶液中得到以三重态机理极化为主的中性杜半醌自由基DQH*和以碳为中心的乙二醇碳自由基R*(OH)2的极化信号,而加入氮氧自由基 TEMPO后,则只观测到极化的TEMPO的E+E/A极化谱,其产生机理属于以四重态为先驱的自由基-三重态对极化机理(QP-RTPM),结合极化强度的理论计算对该体系的极化形成过程进行了分析.     

三重态/氢给体分子/TEMPO体系CIDEP超精细相关性的研究

利用高时间分辨ESR波谱仪研究了二重态自由基和三重态分子之间相互作 用产生的CIDEP(化学诱导动态电子极化),探讨了此类体系中自由基的CIDEP信号的超精细相 关性,认为这种超精细相关性是由于自由基和三重态分子的超精细相互作用引起的。     

吸收型自由基-三重态对的电子极化强度理论计算

激光照射荧光蒽／氮氧自由基／苯体系可得到氮氧自由基的A+A／E吸收型CIDEP信号,以自由基与三重态分子相互作用为模型,以自由基-三重态对的二重自旋态优先等量布居为初始条件,用二阶微扰理论和密矩阵运动方程计算了该体系的CIDEP。     

乙二醇均相溶液中苊醌三重激发态淬灭反应的TR-ESR研究

利用时间分辨电子自旋共振(TR-ESR)方法,研究了乙二醇(EG)均相溶液中稳定自由基TEMPO和生物抗氧化剂维生素C(VC)对苊醌(ACQ)激发三重态3ACQ*的淬灭反应.光解ACQ/EG体系,观察到苊醌中性自由基ACQH*和乙二醇烷基自由基的发射/吸收+发射(E/A+E)的CIDEP信号,ACQH*和CH2(OH)CHOH由3ACQ*从EG上夺氢生成.光解ACQ/TEMPO/EG体系,3ACQ*与TEMPO相互作用将极化转移给TEMPO.光解ACQ/VC/EG体系,3ACQ*除了从EG上夺氧外,还从VC上夺氢生成VC负离子基As*-.较强的As*-的CIDEP信号表明VC对3ACQ*有明显的淬灭作用.     

采用高信噪比电磁诱导透明谱测定~(85)Rb原子5D_(5/2)态的超精细相互作用常数

基于~(85)Rb原子5S1/2-5P3/2-5D_(5/2)阶梯型能级系统(780 nm+776 nm),利用高信噪比的电磁诱导透明谱对~(85)Rb原子5D_(5/2)态超精细分裂进行测量.其中,频率校准是通过位相型电光调制器和共焦法布里-珀罗腔共同实现的.通过测量~(85)Rb原子5D′5/2态(F′=5),(F′′=4)及(F′′=3)之间的超精细分裂,我们确定了~(85)Rb原子5D_(5/2)态的磁偶极超精细相互作用常数(A=-(2.222±0.019)MHz)和电四极超精细相互作用常数(B=(2.664±0.130)MHz).     

BaCrSi4O10与AgGaSe2:Cr2+吸收光谱的精细结构及自旋单态对零场分裂参量的影响

在强场图像中构造了四角对称环境中Cr²⁺离子包括自旋单态在内的完全能量矩阵, 通过对角化能量矩阵方法, 计算得到了BaCrSi₄O₁₀与AgGaSe₂:Cr²⁺吸收光谱的精细结构及自旋单态对零场分裂参量的影响. 从理论上给出了BaCrSi₄O₁₀与AgGaSe₂:Cr²⁺吸收光谱的精细结构及BaCrSi₄O₁₀的零场分裂参量值. 计算结果显示自旋单态对零场分裂参量D的影响完全可忽略, 但对a和F的影响比较大. 这种影响主要来自自旋-轨道耦合导致的自旋五重态与自旋三重态和自旋单态的相互作用, 而自旋轨道耦合的选择定则显示自旋单态并非直接影响五重态而是通过自旋三重态间接地影响基态的五重态. 因此, 为了得到准确的零场分裂参量值, 所有的自旋态都应该考虑.     

光解丙酮/乙二醇体系的CIDEP实验研究

紫外激光照射下,用时间分辨电子自旋共振(TRESR)波谱仪研究了光解ACETONE/EG体系的化学诱导动态电子极化(CIDEP),得到了丙酮羰自由基(CH3)2C.OH和乙二醇羰自由基CH2OH C.HOH的发射/吸收(E/A)型极化信号,这是一个RPM极化过程.在胶束环境中,不同表面活性剂以及不同的浓度对体系极化的影响是不同的.阳离子表面活性剂CTAB对体系中生成的自由基的极化机理没有产生显著影响,而加入体系中TX-100的浓度对体系的极化机理却产生了很大的影响.在ACETONE/EG体系中,随着TX-100浓度的增加,TM机理对极化强度的贡献明显增大.     

化学诱导动态电子极化自由基-三重态对理论中选择三重态淬灭的证明

用时间分辨ESR测出的吩噻嗪/2,2,6,6-四甲基哌啶氮氧自由基(TEMPO)光诱导产生的三重态发射CIDEP信号可用Blätter提出的自由基-三重态对机理来解释,由荧光光谱及脉冲激光光声微量量热实验结果直接证明了Bläter理论关于自由基只选择淬灭双重自旋态的自由基/三重态对中的三重态的假设.     

GeFe2O4晶体的基态能级和零场分裂参量

GeFe₂O₄是一种单晶化合物，考虑到由3个〈111〉方向之一的一个 轴，从一个中心位置 到另一个中心位置之间，以Fe²⁺离子为中心离子和O^2-为配体构 成了三角（C 3v）对称体系.利用不可约张量理论，建立了3d⁴/3d⁶离子三角（C3 v）对称的晶体场和 自旋相互作用哈密顿矩阵，因此，由完全对角化的晶体场和自旋-轨道相互作用哈密顿矩阵 和电子顺磁共振理论公式求出单晶GeFe₂O₄中Fe²⁺离子 的电子顺磁共振零场分 裂参量D和F-a.并研究了自旋三重态对电子顺磁共振（EPR）零场分裂的贡献.结果显示自旋 三重态对基态零场分裂的贡献是较强的，理论计算结果与实验值相符. 关键词： 自旋三重态 晶体场 低自旋态 高自旋态 零场分裂     

Theoretical study of the intensity of chemically induce dynamic electron polarization of radical-triplet pairs

Considering the interaction between encited triplet molecule and cloublet radical,based on the second-order perturbation theroy and the motion equation of density matrix,the polarzation intersity of RTPM were theoretically calculated with the overpopulated doublet spin states and quartet spin states of radical0triplet paris as initial conditions the radical result from the zero-field-splitting(zfs)and the multiplet A/E and E/A polarization result from hyperfine (hf) interactions of the triplet molcule,The hyperfine ralated A A/E or E E/A CIDEP on the radical were the overpopulation of the net abscrptive or emissive polarization and multiple A/E or E/A polarization.     

E.P.R. and zero field ODMR studies of the lowest excited triplet states of halogen containing anilines and anisole

The molecular and electronic structures of the lowest excited triplet states of the halogen containing anilines and anisole were studied by means of E.P.R. and zero field ODMR techniques. Single crystal E.P.R. spectra of 4-fluoroaniline and 4-bromoanisole in 1,4-dibromobenzene host show well resolved hyperfine splittings due to halogen nuclei. It is shown that the fluorine hyperfine splitting and the angular dependence of the E.P.R. signal of 4-fluoroaniline can be explained on the basis of the skewed antiquinoid structure of the triplet state. The angular dependence of the E.P.R. signal and the sublevel decay rates of 4-chloroaniline in 1,4-dichlorobenzene also show that the molecule is distorted into an antiquinoid form. The analysis of the bromine hyperfine and quadrupole splittings of 4-bromoanisole indicates that the spin distribution is likely to be similar to that of 4-fluoroaniline.     

NMR paramagnetic relaxation enhancement: test of the controlling influence of zfs rhombicity for S = 1

Prior theoretical work has predicted that the NMR paramagnetic relaxation enhancement (NMR-PRE) produced by electron spin S = 1 ions is highly sensitive to orthorhombic terms in the static zero field splitting (zfs) tensor. Zfs orthorhombicity (which implies chemical inequivalence of the three principal directions of the zfs-principal axis system and is described by the zfs E-parameter) is predicted to suppress the NMR-PRE profoundly relative to the reference cylindrical zfs-limit situation. This expectation was tested experimentally by a comparison of the zfs-limit NMR-PRE produced by [Ni(II)(en)(3)](2+) (en = ethylenediamine), a trigonal complex which lacks zfs-rhombicity, with the zfs-limit NMR-PRE produced by two orthorhombic complexes, [Ni(II)(en)(2)(H(2)O)(2)](2+) and [Ni(II)(en)(H(2)O)(4)](2+). As predicted, the zfs-limit NMR-PRE produced by the orthorhombic complexes in the proton resonance of a dioxane probe species in the solvent was strongly suppressed (by factors of approximately 5 and 7, respectively) relative to the comparable measurement on the trigonal complex. The suppression of the NMR-PRE due to the orthorhombic zfs terms is counteracted by an applied Zeeman field, leading to a predicted rise in the NMR-PRE with increasing Zeeman field strength; this rise occurs when the Zeeman energy is comparable to the orthorhombic zfs splitting, 2E. This second prediction of theory was likewise confirmed: the expected rhombicity-induced magnetic field dependence in the NMR-PRE was observed for the orthorhombic complexes but not for the trigonal complex.     

The magnetic hyperfine fields of rare earth ions in metals

Data for the magnetic dipole hyperfine interaction of essentially single rare earth ions in metals, measured with different experimental methods, are collected and discussed. Depending on the host, the magnetic hyperfine field of these paramagnetic ions remains undisturbed by the environment, or it is enlarged, or weakened or can even become completely lost. If there are magnetic ions in the neighbourhood, the magnetic interaction can enlarge the hyperfine field of the single ion by a transferred hyperfine field. The reason of the demagnetization effect may be crystal field splitting and hybridization. The core polarization field of the free rare earth ions is redetermined from measurements of the hyperfine interaction in nonmagnetic metals at low magnetic ion concentration.     

Dynamic nuclear polarization with single electron spins

We polarize nuclear spins in a GaAs double quantum dot by controlling two-electron spin states near the anticrossing of the singlet (S) and m(S)= +1 triplet (T+) using pulsed gates. An initialized S state is cyclically brought into resonance with the T+ state, where hyperfine fields drive rapid rotations between S and T+, "flipping" an electron spin and "flopping" a nuclear spin. The resulting Overhauser field approaches 80 mT, in agreement with a simple rate-equation model. A self-limiting pulse sequence is developed that allows the steady-state nuclear polarization to be set using a gate voltage.     

Hyperfine anomaly arising from the nuclear spin-forbidden transition,and absolute sign determination of the zero-field splitting constant

It has been found in the triplet E.S.R. spectra of radical pairs in irradiated potassium deuterium fumarate that the hyperfine structure of the two transitions, M _s = 1?0 and M _s = 0?+1, are entirely different. This anomaly has been interpreted in terms of the forbidden transition arising from the mixing of the nuclear spin states by the anisotropic hyperfine interaction. The theory has been developed for multiplet electron spin systems and includes the nuclear Zeeman interaction which is often neglected. The theoretical predictions are in good agreement with the observed separations and intensities of the anomalous hyperfine lines. In addition, it has been found that since the forbidden lines of the electron spin multiplet system with S ≥ 1 appear strongly only in transitions which include some specific electronic spin states, the anomalous features of the spectra make it possible to determine the absolute sign of the zero-field or hyperfine splitting constant, if the sign for one of them is known. Using this principle, attempts have been made to determine the absolute sign of the zero-field splitting constant for a number of triplet E.S.R. spectra which exhibit a hyperfine anomaly arising from the proposed mechanism.     

超精细结构效应对辐射光谱圆极化特性的影响

在相对论多组态Dirac-Fock方法和密度矩阵理论的基础上,利用发展的全相对论扭曲波程序,系统研究了超精细结构效应对纵向极化电子碰撞激发过程以及退激发辐射光谱圆极化特性的影响.计算得到了类氦Sc~(19+)和~(205)Tl~(79+)离子1s~2 ~1S_0→1s2p ~3P_2超精细结构层次上M_F能级的碰撞强度,考察了辐射衰变过程中发出特征光子的极化特性,并分析了E1-M2量子干涉效应以及电子-电子间相互作用的相对论修正对退激发辐射光子圆极化度的影响.     

High pressure Mössbauer study of hyperfine interactions in europium metal

The 21.6 keV Mössbauer resonance of ¹⁵¹Eu has been studied at 4.2 K in europium metal at pressures up to 16 kbar. The measured pressure coefficient of the isomer shift dS/dp = 4.8 (5) × 10^-2 mm/sec kbar can be understood as a congruent compression of 6s conduction electrons. The magnetic hyperfine splitting decreases under pressure. The slope of the (negative) hyperfine field dB/dp = + 0.133(8) T/kbar must arise predominantly from an increase in the conduction electron polarization.     

Electron and nuclear spin interactions in the optical spectra of single GaAs quantum dots

Fine and hyperfine splittings arising from electron, hole, and nuclear spin interactions in the magneto-optical spectra of individual localized excitons are studied. We explain the magnetic field dependence of the energy splitting through competition between Zeeman, exchange, and hyperfine interactions. An unexpectedly small hyperfine contribution to the splitting close to zero applied field is described well by the interplay between fluctuations of the hyperfine field experienced by the nuclear spin and nuclear dipole/dipole interactions.