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.     

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.     

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.     

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).     

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.     

Ground State and Spin-Glass Phase of the Large-N Infinite-Range Spin Glass via Supersymmetry

The large-N infinite-range spin glass is considered, in particular, the number of spin components k needed to form the ground state and the sample-to-sample fluctuations in the Lagrange multiplier field on each site. The physical significance of k for the correlation functions is discussed. The difference between the large-N and spherical spin glass is emphasized; a slight difference between the average Lagrange multiplier of the large-N and spherical spin glasses is derived, leading to a slight increase in the energy of the ground state compared to the naive expectation. Further, there is a change in the low-energy density of excitations in the large-N system. A form of level repulsion, similar to that found in random matrix theory, is found to exist in this system, surviving interactions. Even though the system is an interacting one, a supersymmetric formalism is developed to deal with the problem of averaging over disorder.     

Tuning of the Electron Spin Relaxation Anisotropy via Optical Gating in GaAs/AlGaAs Quantum Wells

The carrier-density-dependent spin relaxation dynamics for modulation-doped GaAs/Al_(0.3)Ga_(0.7)As quantum weiis is studied using the time-resolved magneto-Kerr rotation measurements.The electron spin relaxation time and its in-plane anisotropy are studied as a function of the optically injected electron density.Moreover,the relative strength of the Rashba and the Dresselhaus spin-orbit coupling fields,and thus the observed spin relaxation time anisotropy,is further tuned by the additional excitation of a 532 nm continuous wave laser,demonstrating an effective spin relaxation manipulation via an optical gating method.     

Ultrafast Quantum Relaxation Dynamics of Magnetically Ordered Systems with Spin Crossover in an Excited State under a Sudden Perturbation

JETP Letters - A theoretical model based on the relaxation equation for the density matrix has been proposed to describe the ultrafast time dynamics of magnetically ordered systems with spin...     

Observation of Electron Spin Resonance in the Microwave-Induced Photovoltage

JETP Letters - The microwave-induced photovoltage in two-dimensional electron systems in an AlAs quantum well and a ZnO/MgZnO heterojunction under the conditions of the quantum Hall effect is...     

Discovery of the First 2- State in 16C via Neutron Knockout Reaction

The ¹⁶C nucleus has been investigated by the neutron knockout reaction of ¹⁷C on a liquid hydrogen target. Applying the invariant mass method in inverse kinematics and γ-ray spectroscopy, the energy spectrum was reconstructed by triple-coincidence measurement, in which neutrons, charged fragments, and γ rays from the decay of the reaction residue (¹⁶C*) were detected. A peak at 0.47 MeV was observed in the invariant mass spectrum in coincidence with a peak at 0.74 MeV in the γ-ray spectrum, which indicates the presence of an unbound state with an excitation energy of 5.46 MeV. Comparison of the experimental cross section with the value derived by a theoretical calculation provided evidence that the spin-parity of this state is 2^?.     

Oscillations of the Degree of Circular Polarization in the Optical Spin Hall Effect

The optical spin Hall effect appears when elastically scattered exciton polaritons couple to an effective magnetic field inside of quantum wells in semiconductor microcavities. Theory predicts an oscillation of the pseudospin of the exciton polaritons in time. Here, we present a detailed analysis of momentum space dynamics of the exciton polariton pseudospin. Compared to what is predicted by theory, we find a higher modulation of the temporal oscillations of the pseudospin. We attribute the higher modulation to additional components of the effective magnetic field which have been neglected in the foundational theory of the optical spin Hall effect. Adjusting the model by adding non-linear polariton-polariton interactions, we find a good agreement in between the experimental results and simulations.