On the calculation of <H 2> molecular integrals

The density matrix equations of motion arising in the triplet mechanism of chemically induced electron spin polarization are solved exactly without the imposition of the Redfield approximation. It is shown that the triplet spin relaxation time occurring in the final expression is not the true relaxation time because the spectral density involved depends both on the rotational correlation time and on the quenching rate. The effective spin relaxation time differs only slightly from the true time. The equations are extended to the case where the initial triplet passes on its polarization to the secondary triplet and exact solutions for the polarizations of the latter's doublets are obtained in the form Π_B = cΠ_A; an explicit expression for c is presented. The consequences of the secondary triplet being able to pass back its polarization to the initial triplet are explored and a ‘coherence effect’ on the polarization on the first triplet's doublets is analysed.     

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.     

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。     

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.     

Magnetic field dependence of the deactivation rates of triplet azocumene in solution

The triplet sensitized photo-decomposition of azocumene into nitrogen and cumyl radicals is investigated by time resolved EPR and optical absorption spectroscopy. It is found that the cumyl radicals carry an initial spin polarization and are formed with a yield that depends on both the solution viscosity and the strength of an external magnetic field. The phenomenon is interpreted in terms of a depopulation-type triplet mechanism, i.e. a competition between decay into radicals and fast, triplet sublevel selective intersystem crossing (ISC) back to the azocumene ground state. Analysis of the data yields relative rate constants for the ISC processes and the cleavage reaction of triplet azocumene. The energetically lower zero field triplet substate is depopulated by ISC about seven times faster than the upper one and about two orders of magnitude faster than depopulation by cleavage occurs. Cleavage probably takes place on the nanosecond time scale, while the ISC must proceed on the picosecond scale, as at elevated viscosity it becomes faster than the rotational Brownian motion of the molecule.     

The first observation of electron spin polarization in the excited triplet states caused by the triplet-triplet annihilation

The spin polarization of excited triplet states caused by mutual annihilation of triplet states was detected by time-resolved electron paramagnetic resonance (EPR) of triplet excitons in two molecular crystals, anthracene-tetracyanobenzene and phenazine-tetracyanoquinodimenthane. The time profile of the two EPR lines of the triplet exciton spectrum have been studied in the time range up to 200 μs after a laser pulse. Besides the initial polarization of the lines, due to intersystem crossing, a long-lasting polarization process is detected which is attributed to the triplet-triplet annihilation. The investigation of the dependence of the phenomenon on the intensity of the light pulse and on the orientation of the crystals in the magnetic field is presented.     

The line shapes of a tumbling triplet

The line shapes of a triplet spin system which interacts simultaneously with the molecular environment and with an externally applied field depend on the relative strengths of these interactions and on the motion of the molecule relative to the laboratory. In this paper line shapes are reported for zero, low, intermediate and strong applied fields, assuming that the molecular motion is due to strong collisions and that the tumbling rate is slow or intermediate.     

Stimulated Electron Spin Polarization in Strongly Coupled Triplet–Doublet Spin Pairs

The possibility of stimulating electron spin polarization in a system consisting of a stable paramagnetic center and a chromophore that can be excited into its triplet state is discussed. In such systems, the doublet state of the paramagnetic center couples to the excited triplet state of the chromophore and if the coupling is larger than the difference in the precession frequencies of the doublet and triplet, the eigenstates of the coupled system are quartet and doublet states. The quartet state is usually the lowest energy excited state. Following light excitation, the initial electronic relaxation to the quartet state generates strong multiplet polarization if it is governed by the spin–orbit coupling that follows the molecular symmetry. It is shown that application of a selective π-pulse to the ±3/2 ↔ ±1/2 transitions of the quartet converts this multiplet polarization into net polarization. The magnitude and orientation dependence of the generated polarization is estimated on the basis of a simple analytical model. The experimental conditions required for this net polarization to be retained in the ground state after decay of the quartet state are discussed. The viability of using this as a method to enhance the signal strength of a spin label or metal center in selective excitation experiments is considered.     

Photocleavage reaction of bromine substituted aromatic acyl compounds studied by CIDEP and transient absorption spectroscopy

The photocleavage of the CBr bond in bromoacetylnaphthalene is investigated by transient absorption and time resolved EPR spectroscopy. In the transient absorption of 2-bromo-2′-acetylnaphthalene, the absorption band observed at λ_max ~440 nm is assigned to the triplet state of the parent molecule. After decay of the triplet absorption, a long lived absorption band is observed at λ_max ~380 nm, which is assigned to naphthoylmethyl radical. The yield of this radical is not dependent on the concentration of oxygen even though the absorption band of the triplet state was quenched by addition of oxygen. Thus we conclude that the spin multiplicity of the precursor molecule is singlet. The CW time resolved EPR spectrum shows a typical E?/A CIDEP pattern of three hyperfine lines of the naphthoylmethyl radical. This result suggests some contribution from triplet precursor molecules. However, a careful analysis of the time profile of the CIDEP intensity observed by FT-EPR revealed that the polarization is generated from the radical pair mechanism (RPM) from the encountered pair of two free naphthoylmethyl radicals and the radical-triplet pair mechanism. RPM polarization by the geminate radical pair, formed by the Br atom and the naphthoylmethyl radical, is not observed. This fact indicates that large spin-orbit coupling (Δg and/or fast spin relaxation by g anisotropy) spoils the RPM polarization. The finding is in contrast to the recent observation of RPM polarization in the Cl cleavage reaction of 1-(chloromethyl)naphthalene.     

Dynamic nuclear polarization in pulsed ENDOR experiments

Properly prepared pulse sequences of microwave and radio frequency have been employed to investigate the effect of polarization transfer from the polarized photo excited triplet state of pentacene in p-terphenyl crystals to the surrounding protons in pulsed ENDOR experiments. The ENDOR signal, measured as the change of electron spin echo (ESE) amplitude, is affected by the mode of RF pulses. When B0 parallelx (the long molecular axis), the ESE amplitude of the high-field transition of the triplet state changes from the maximum positive to zero with a pi RF pulse, and to the maximum negative with a 2pi pulse, while that of the low-field transition changes from nearly zero to the maximum negative as the RF pulse width increases. The effect is attributed to the strong electron spin polarization produced in the creation of the photoexcited triplet state and the subsequent efficient electron- nuclear polarization transfer process.     

Time-resolved EPR study of electron spin polarization and spin exchange in mixed solutions of porphyrin stable free radicals

The time-resolved electron paramagnetic resonance (EPR) spectra are studied in the temperature range of 110–300 K for two mixed solutions of porphyrins, ZnTPP and H₂TPP, in toluene and the stable free radical 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO). The EPR spectra and their kinetic behavior were studied for concentrations of TEMPO varied in the interval from 0.51 to 7.68 mM, while the porphyrin concentration was fixed as 1 mM. The EPR spectra of triplet-state porphyrins and free radicals manifest the chemically induced spin polarization. For the relatively short-lived radical-triplet pairs, with the perturbation theory up to the fourth order, the theoretical expressions are obtained for the triplet and radical spin polarization induced by the enhanced intersystem crossing (ISC) due to the interaction of excited singlet-state porphyrins with free radicals and by the triplet quenching by free radicals. The time-dependent EPR spectra of the triplets are simulated taking into account the spin-lattice relaxation. It is shown that the variation of the triplet EPR spectra shape, when the time of observation increases, arises from the spin-lattice relaxation kinetics. The kinetic behavior of the TEMPO EPR spectrum was simulated on the basis of the kinetic scheme suggested earlier in the literature. The triplet spin-lattice relaxation time, the rate of the ISC and the lifetime of the excited singlet state were estimated by fitting the kinetic curves for the triplet EPR spectra intensity. For the mixed porphyrin-TEMPO solutions, a possible set of the rate constants of important bimolecular processes were determined. For this set of parameters, it turns out that the spin polarization transfer has a smaller rate constant than the rate constant of the diffusion collisions of the triplet and radical. It appears that the rate constant of the ISC catalyzed by radicals is relatively high in the solutions close to the melting point of the solvent and in the soft-glassy state. In the triplet porphyrins the initial spin polarization induced by the spin-selective ISC was found to exceed the equilibrium spin polarization by up to two orders of magnitude.     

Electron spin polarization in an excited triplet-radical pair system: Generation and decay of the state

A computational model to simulate electron spin polarization in the three-spin-1/2 system composed of the molecular excited triplet state of (tetraphenylporphinato)zinc(II) (ZnTPP) and the doublet ground state of the 3-(N-nitronyl-notroxide) pyridine (3-NOPy) stable radical is proposed. The model is based on numerical solutions of the stochastic Liouville equation for the diffusively rotating system where the magnetic dipolar, isotropic Heisenberg exchange, and anisotropic Zeeman electron spin interactions are taken into account in a full measure, whereas the intersystem crossing processes between the singlet and triplet states of ZnTPP are considered in terms of kinetic equations for the relevant spin density matrices. Additional longitudinal and transversal paramagnetic relaxation caused by relative rotation motions of the ZnTPP and 3-NOPy moieties is taken into consideration in the form of the generalized relaxation operator.     

Rotational correlation functions of single molecules

Single molecule rotational correlation functions are analyzed for several reorientation geometries. Even for the simplest model of isotropic rotational diffusion our findings predict nonexponential correlation functions to be observed by polarization sensitive single molecule fluorescence microscopy. This may have a deep impact on interpreting the results of molecular reorientation measurements in heterogeneous environments.     

自旋极化有机电致发光器件中单线态与三线态激子的形成及调控

由于有机半导体（OSC）材料自旋弛豫时间长、自旋扩散长度大,OSC自旋器件逐渐成为研究热点.对于有机电致发光器件（OLED）,通过自旋极化电极调控单线态和三线态激子比率是提高其效率的有效方法.本文从漂移扩散方程和载流子浓度连续性方程出发,结合朗之万定律建立了一个自旋注入、输运、复合的理论模型.计算了OSC中的极化电子、空穴浓度,得出了单线态和三线态激子的比率.分析了电场强度、自旋相关界面电导、电极和OSC电导率匹配和电极极化率等因素的影响.计算结果表明：两电极注入反向极化的载流子并提高载流子自旋极化率,有     

Role of highest occupied molecular orbitals in molecular field-free alignment by a femtosecond pulse

This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent Schr?dinger equation. The broad rotational wave packets excited by the femtosecond pulse are defined in conjugate angle space, and their coefficients are obtained by solving a set of coupled linear equations. Both single molecule orientation angles and an ensemble of O₂ and CO molecule angular distributions are calculated in detail. The numerical results show that, for single molecule highest occupied molecular orbital (HOMO) symmetry σ tends to have a molecular orientation along the laser polarization direction and the permanent dipole moment diminishes the mean of the orientation angles; for an ensemble of molecules, angular distributions provide more complex and additional information at times where there are no revivals in the single molecule plot. In particular, at the revival peak instant, with the increase of temperature of the molecular ensemble, the anisotropic angular distributions with respect to the laser polarization direction of the π _g orbital gradually transform to the symmetrical distributions regarding the laser polarization vector and for two HOMO configurations angular distributions of all directions are confined within a smaller angle when the temperature of the molecular ensemble is higher.     

The spin density matrix for slowly reorienting molecules in zero field

The time evolution of the spin density matrix of a spin embedded in a slowly moving molecule is investigated using Gordon's extended diffusion model for molecular reorientation and allowing the spin to follow the molecular motion. The results for this model are identical with those previously obtained using a jump diffusional model and do not give the adiabatic limit in slow motion. This model is valid provided the molecular angular velocity correlation time is short compared to the spin precession period. The perturbed angular correlation of rays or the spin resonance line shape can be calculated for any value of the rotational diffusion constant by diagonalizing a finite matrix. The necessary matrix elements are given for the 247 keV state of ¹¹¹Cd (I = 5/2).     

Prohibition of ortho-para transitions in a water molecule

A theoretical consideration is given to three types of prohibition of transitions between the rotational states of spin isomers of an H ₂ ¹⁶ O molecule, which are based on the molecular symmetry. This is the symmetry of the electron shell of the molecule, of the proton spin functions, of the spatial position of molecular nuclei, and of the rotational Hamiltonian. The prohibition of dipole transitions between isomers and the prohibition of transitions on the basis of the Pauli principle were known earlier. Another prohibition exists which is a consequence of the symmetric position of protons relative to the oxygen nucleus. Conditions are indicated under which the prohibition of ortho-para transitions in a water molecule disappear. In the general form these conditions are realized when the molecule loses the above-listed symmetries. Transitions are allowed in the dipole approximation if the proton spin moments are free and do not form superposition states and the O-H bond lengths are different because of nonlinearity of the molecular vibrations. The transitions are induced by the dipole-moment component due to the deformation of the electron shell of the molecule.     

Molecular symmetry as an aid to geometry determination in ligand protein complexes

Dipole-dipole couplings between pairs of spin 12 nuclei, which can be measured from NMR spectra in field-ordered media, offer useful constraints on the orientation of various fragments in molecular systems. However, the orientation of fragments relative to a molecule fixed reference frame is often key to complete structure determination. Here, we demonstrate that the symmetry properties of molecular complexes can aid in the definition of a reference frame. It is shown that a threefold rotational symmetry axis dictates the direction and symmetry of the experimentally determined order tensor for alpha-methyl-mannose in fast exchange among the three symmetry-related binding sites of mannose binding protein. This approach facilitates studies of the geometry of the ligand in the protein-ligand complex and also may provide a novel route to structure determination of a homomultimeric protein.     

Enhancement of efficiency in photo-excitation to the triplet state by laser-pulse reshaping

An optical system is proposed to enhance efficiency in photo-excitation to the triplet state by reshaping an original laser pulse into a train of pulses. This optical system can be used to improve the attainable nuclear spin polarization in dynamic nuclear polarization experiments using photo-excited triplet electron spins.     

Coherent laser spectroscopy of RF resonances in liquid

Four-photon polarization spectra of double distilled water subjected to a special treatment in a cavitation chamber and 20% aqueous solution of hydrogen peroxide were recorded in the range ±8 cm⁻¹. All recorded spectra contain narrow (< 0.3 cm⁻¹) resonances corresponding to the frequencies of the rotational spectrum of ortho and para spin isomers of the H₂O molecule. Numerical simulation of the spectra obtained made it possible to quantitatively estimate the contribution of the rotational spectrum to the coherent scattering signal. It was found that the contribution of the para spin isomer of the H₂O molecule to the rotational line spectrum decreases in an aqueous solution of the α-chymotrypsin protein. Apparently, this decrease indicates the selectivity of interaction of biopolymer molecules with different spin isomers.