Optical and time-resolved EPR studies of the excited states of azastilbenes and their protonated cations

The effects of protonation on the excited states oftrans-3-styrylpyridine (StP) andtrans-4,4′-dipyridylethylene (DPE) have been studied through measurements of the time-resolved electron paramagnetic resonance (EPR), ultraviolet absorption, and fluorescence spectra in methanol-water mixtures at 77 K. The assignment of the transient EPR signals was carried out with the aid of the stretched poly(vinyl alcohol) films method. From the analysis of these spectra it is concluded that the single protonation appears to have little effect on the zero-field splitting parameters and the anisotropy in the sublevel populating rates of the lowest excited triplet (T₁) states of StP and DPE. However, the decay rate constants of the fluorescent states decrease and fluorescence quantum yields increase on single protonation. These experimental results suggest that the single protonation causes a decrease in the intersystem crossing (ISC) rates for the three T₁ sublevels. These results are explained in terms of the vibronic mixing between the¹nπ* and¹ππ* states in the lowest excited singlet state. The assignment of StP to the specified conformer was carried out through the analysis of the anisotropic ISC processes.     

Chemically induced dynamic electron polarization of C60 nitroxide bisadducts and spin multiplicity of their excited states

A series of biradicals consisting of a C₆₀ linked to two nitroxide addends have been studied by time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy. The series includes all four trans bisadducts and the equatorial isomer. After a visible laser pulse, the bisadducts in toluene liquid solution show chemically induced dynamic electron polarization (CIDEP) effects with a complex pattern of narrow lines in emission and enhanced absorption. From the knowledge of the sign of exchange interaction between the two nitroxide moieties, it was possible to account for the CIDEP effect in terms of an intramolecular triplet-triplet annihilation. A broad signal attributed to the quintet excited state was observed at short time delay after the laser pulse. The TR-EPR spectra recorded at low temperature in glassy matrix are assigned to an excited triplet state localized on the C₆₀, with a small interaction with the spins of the two nitroxide fragments. The assignment is based on spectral simulation and analysis of the transient nutation frequency. The small exchange interaction between excited triplet C₆₀ and nitroxide is shown to depend on the nature of the nitroxide addend.     

Synthesis and Structural, Magnetic and EPR Characterization of Discrete Finite Antiferromagnetic Chains

The synthesis, magnetic and electron paramagnetic resonance (EPR) characterisation of isolated, discrete, {Cr _n ^III } antiferromagnetically coupled chain complexes is reported for n = 6 and 7. Previous studies had reported supramolecular linked {Cr _n ^III } _x species. For n = 6, the lowest lying total spin state is diamagnetic with S = 1 and 2 first and second excited states, respectively; for n = 7, the lowest lying total spin state is S = 3/2 with S = 1/2 and 5/2 first and second excited states, respectively. The zero-field splittings of these states are well defined by low-temperature, multi-frequency EPR spectroscopy.     

Angle-selective measurements of spin soliton in ladder polydiacetylene by pulsed 94 GHz EPR

Angle-selection experiments of a spin soliton in randomly oriented ladder polydiacetylene were carried out by pulsed electron paramagnetic resonance (EPR) at W-band. EPR measurement using 94 GHz microwaves increased the difference in the resonance field due tog anisotropy of the spin soliton to allow the orientation dependence of transient nutation, electron nuclear double resonance (ENDOR) and spin relaxations to be investigated. The shape of theg anisotropy-resolved nutation spectrum was discussed on the basis of the EPR transition moments and the differences between spin relaxation times. Reliable assignments of hyperfine couplings to the β protons (H_β) of the alkyl side chains were achieved with the support of W-band ENDOR measurements. No significant orientational dependence in theT ₁ andT ₂ processes was found in terms of isotropy of the H_β-hyperfine interaction.     

Structure of excited states in Se-isotopes

Energy systematics of the anomalously low-lying excited 0⁺ states and the systematic behaviour of theB(E2: 0⁺→2 ₁ ⁺ ) values in Se-isotopes are investigated by taking the important effect of mutual interplay between dynamical pairing and quadrupole correlations into account.     

High spin states in205Pb and a precision test of the nuclear shell model for three nucleons

Using the²⁰⁴Hg(α, 3n) reaction withα-particles of about 40 MeV, we have proved by applying nowadays conventionalγ-ray spectroscopy in-beam technique, that there are two isomeric states in²⁰⁵Pb at the excitation energies 5,161.3 and 3,195.5 keV having the half-lives 71±3 and 217±5 ns, respectively. These isomeric states have spins and parities 33/2⁺ and 25/2^? and are mainly due to thei ₁₃ ^2/?3 andi ₁₃ ^2/?2 p ₁ ^2/?1 configurations, respectively. This conclusion is supported by the experimentalg-factors of these states being ?0.159±0.008 and ?0.0676±0.0011, respectively. It is furthermore shown that theE2 effective neutron charge is the same forE2 transitions from the 33/2⁺ state in²⁰⁵Pb and from the 12⁺ state in²⁰⁶Pb as required by the assumption that the²⁰⁸Pb core is responsible for the totalE2 strength of the neutron holes, and that these states are due to thei ₁₃ ^2/?3 andi ₁₃ ^2/?2 configurations. The calculatedB(E3) values ofE3 transitions from isomeric states in²⁰⁵Pb and²⁰⁶Pb agree reasonably well with the experimental values as expected from the assumption that theE3-strength should come from particle coupling to the octupole states of the²⁰⁸Pb core. The energies of the six most well established excited states in²⁰⁵Pb with angular momenta in the region 19/2–33/2 were calculated using empirical single-particle energies, empirical two-particle interactions and angular momentum algebra. The average deviation between experimental and calculated energies is ?3 keV and the root mean square deviation 6 keV as compared to the uncertainty ± 5 keV in the nuclear masses used in the calculation. For the orbits concerned the shell model is thus valid with an extremely high precision. The contribution of effective three-particle interaction in these orbits must consequently be less than about 5 keV.     

Spin alignment and polarisation in the (16O,15N) transfer reactions

The spin alignment of the¹⁵N ₃ ^2/* (6.33 MeV) state was measured in the⁸⁸Sr(¹⁶O,¹⁵N)⁸⁹Y reaction atE _L =96 MeV using theγ-recoil method. Angular distributions of excited states in¹⁵N and⁸⁹Y were measured with high accuracy. The analysis in terms of DWBA shows that the spin alignment is correctly described by the usual reaction models. The polarisation of the outgoing¹⁵N_1/2(GS) and¹⁵N ₃ ^2/* (6.33 MeV) is discussed. It is shown that cross section differences for transitions to final states with different configurations are sensitive to a spin-orbit potential of¹⁵N. The strength and sign of the spin-orbit potential for¹⁵N is determined.     

High-spin states in the single-closed-shell nucleus 142Nd

The excited states of ¹⁴²₆₀Nd₈₂ have been studied using the ¹⁴⁰Ce(α, 2nγ)¹⁴²Nd and ¹⁴²Ce(α, 4γ)¹⁴²Nd reactions. Singles γ-ray, γ-γ coincidence spectra and angular distributions of γ-rays with respect to the beam direction have been measured. Excited states up to 6.7 MeV with spin values up to 14 are populated. The energy spacings between the lower excited states with spin values up to 8 are similar to those found in the lighter N = 82, even-Z isotones. The majority of the observed states with spin values up to 10 can be explained as two-quasiparticle states. Several of the highest-spin states can be explained qualitatively as fourquasiparticle states. Strong population of the highest excited states (at about 5.7 MeV) is noted, like in other N = 82 isotones. The observed levels in ¹⁴²Nd are compared with the shell model predictions using a simple δ-force interaction between two nucleons.     

Study of the excited 0+ states through conversion electron spectroscopy of neutron rich Zr and Mo fission products

A windowless Si(Li) electron detector has been used in conjunction with the gas filled fission product separator JOSEF to study totally converted transitions in Zr and Mo isotopes. The existence of twoβ-decay modes in⁹⁶Y,⁹⁸Y and¹⁰⁰Nb is confirmed. The half-lives of theβ-decaying levels feeding O ₂ ⁺ states in⁹⁶Zr and⁹⁸Zr are 6.0 ± 0.4 sec and 0.60±0.05 sec respectively. A search for other first excited O ₂ ⁺ states shows that no such states are apparent in¹⁰⁰Zr and¹⁰⁴Mo.     

Effective field and the Bloch-Siegert shift at bichromatic excitation of multiphoton EPR

The dynamics of multiphoton transitions in a two-level spin system excited by transverse microwave and longitudinal RF fields with the frequencies ω_mw and ω_rf, respectively, is analyzed. The effective time-independent Hamiltonian describing the “dressed” spin states of the “spin + bichromatic field” system is obtained by using the Krylov-Bogoliubov-Mitropolsky averaging method. The direct detection of the time behavior of the spin system by the method of nonstationary nutations makes it possible to identify the multiphoton transitions for resonances ω₀ = ω_mw + rω_rf (ω₀ is the central frequency of the EPR line, r = 1, 2), to measure the amplitudes of the effective fields of these transitions, and to determine the features generated by the inhomogeneous broadening of the EPR line. It is shown that the Bloch-Siegert shifts for multiphoton resonances at the inhomogeneous broadening of spectral lines reduce only the nutation amplitude but do not change their frequencies.     

Measurement of excited state number densities of oxygen and nitrogen in a non-equilibrium plasma

Number densities of several excited states of atomic oxygen and nitrogen have been measured in the decaying non-thermal plasma of a θ-pinch afterglow. The spatial variation of the electron density and temperature as functions of time after initiation of main bank discharge have also been measured to facilitate a comparison of the excited state number densities with model calculations. Measurements of the atomic oxygen excited states indicate that quintet to triplet spin exchange collisions and doubly excited states must be included in the model. The measured populations of the excited atomic nitrogen states agree well with those calculated at high density (N_e≈ 10¹⁴ cm^?3), but disagree badly at lower densities (N_e ≈ 10¹² cm^?3). The discrepancies seem to be real since they are larger than expected measurement uncertainty.     

The deformation of the ground and excited states in the Ag and Sn nuclei

The microscopic calculation of the potential energies in the ground and excited states of Ag and Sn nuclei has been performed. The single particle Nilsson potential and the shell correction Strutinski method have been used. The weak sensitivness to nonaxial deformation has been found for even neighbours of these nuclei. The small tendency towards prolate deformation of the ground and excited one-quasiparticle states originating from theg _9/2 proton subshell in^101–105Ag odd isotopes has been noticed. The behaviour with quadrupole e and hexadecapole ε₄ deformation of the ground and two-quasiparticle excited 0⁺ states originating from thed _5/2,g _9/2 andg _7/2 proton subshells andh _11/2 neutron subshell in^112–118Sn has been investigated. The small quadrupole deformation of the excited 0⁺ states has been found what is in agreement with the experimental data concerning the rotational bands build on the first excited 0⁺ states in Sn isotopes.     

High spin states in153Er

High spin states in¹⁵³Er have been populated in the¹⁴⁴Sm(¹²C, 3n)¹³³Er reaction. Excitation functions, lifetimes, angular distributions,γ-γ coincidences and internal conversion coefficients were measured. Three isomeric states at 2.75 MeV (T _1/2=400 ns), 2.95 MeV (T _1/2～10 ns) and 5.2 MeV (T _1/2=200 ns) have been observed. A fourth isomer seems to be weakly excited above 6.8 MeV. The level scheme proposed is discussed in term of the nuclear shell model.     

Disparity of measured gyromagnetic ratios of ground- and excited-band states in184W

Gyromagnetic ratios of levels in the ground-band and of the 2 ₂ ⁺ state in¹⁸⁴W were measured by means of the transient magnetic field perturbedγ-ray angular distribution technique. The levels of interest were Coulomb excited by beams of 220-MeV⁵⁸Ni and⁶³Cu ions. The results show theg-factor of the 2 ₂ ⁺ state to be approximately half the effectively constant value found for the ground-band levels. This disparity is compared with those previously obtained for the corresponding states in^188–192Os and¹⁸⁶W; these are discussed in the context of the interacting boson model.     

High spin states in128Ba

High spin states of¹²⁸Ba have been investigated by means of the OSIRISγ-spectrometer with 6 asymmetric anti-compton shields and one additional germanium detector. The¹¹⁰Pd(²²Ne, 4n) reaction was used at 96 MeV. Several new high spin states and a new band have been established. The onset of the ph ₁₁ ^2/2 nh ₁₁ ^2/2 4 quasiparticle band has possibly been found.     

High-spin states in107Sn

High-spin states in¹⁰⁷Sn were studied using the reaction⁵⁴Fe(⁵⁶Fe, 2pn)¹⁰⁷Sn. An odd-parity band was identified as based on thevh _11/2 orbit by measuring theγ-ray linear polarization. Also were confirmed the excited states based on thevd _5/2 andvg _7/2 orbits. The halflives of the 17/2⁺ and 11/2^? states were measured to be 0.25(4) ns and 28(11) ps, respectively. The experimental level structure and its interpretation were in good agreement with a shell model calculation.     

Magnetic moments of the 2 1 + states in102, 104Mo

Theg factors of the first excited 2⁺ levels in the neutron-rich nuclei¹⁰²Mo and¹⁰⁴Mo have been studied through the measurement of the perturbed angular correlations for theγ-γ cascades between the 0 ₂ ⁺ -2 ₁ ⁺ -0 ₁ ⁺ level sequences. The results of g=0.42±0.07 for¹⁰²Mo and ofg= _?0.11 ^+0.12 for¹⁰⁴Mo agree with the prediction of the vibrational-rotational model. In terms of IBA, with the assumption ofN _π=3 for the Mo isotopes which takes into consideration a two particle, two-hole excitation across the Z=40 subshell, the proton-bosong factor is deduced to beg _π=1.00±0.23. It is shown that this value provides evidence for subshell effects in¹⁰⁰Zr.     

Pion photoproduction on197Au to ground and isomeric states in197Hg

The lifetime of the 331.3 keV 0 ₂ ⁺ state in¹⁰⁰Zr has been measured at the gas-filled recoil separator for fission products JOSEF. By observing the delayed coincidences between theβ-particles populating the level and theE0 conversion electrons from its decay into the ground state, a half-life of 3.37±0.30 ns has been obtained. From the measured lifetime and the relative intensities of the 0 ₂ ⁺ →0 ₁ ⁺ and 0 ₂ ⁺ →2 ₁ ⁺ transitions, values of 0.493±0.015 for theE0 strength parameterρ, and of 16 single particle units forB(E2,2 ₁ ⁺ → 0 ₂ ⁺ ) have been deduced. The enhanced nature of theE0 transitions suggests mixing of the 0 ₁ ⁺ and 0 ₂ ⁺ states which may be estimated by comparing the experimentalB(E2) values for the 2 ₁ ⁺ →0 ₁ ⁺ and 2 ₁ ⁺ →0 ₂ ⁺ transitions with the predictions of the asymmetric VMI model.     

Yrast states in the doubly-odd nucleus100Tc

High spin states up toJ=14 and excitation energy up toE ^*=3076 keV have been observed in the odd-odd nucleus¹⁰⁰Tc with the reaction⁹⁶Zr(⁷Li, 3n), at bombarding energies between 21 and 31 MeV, by in-beam γ spectroscopy and conversion-electron measurements. A ΔJ=1 negative parity band similar to that observed in theN=57 isotone¹⁰²Rh, and based on the 8^?, 708 keV state has been identified. The observed band can be interpreted in terms of collective core excitations based on a two-quasiparticle state of(πg_9/2 ? νh_11/2) configuration. Comparison with IBFM-2 calculations have been performed.     

Level structure of106Mo

The level scheme of the very neutron rich nucleus ₁₀₆ ⁴² Mo₆₄ has been studied for the first time through theβ decay of¹⁰⁶Nb. Six new excited states were observed inγ singles andγ-γ coincidence experiments in addition to the 2⁺, 4⁺ and 6⁺ members of the ground state band. The excitation energies and the deexcitation pattern suggest the interpretation of the levels at 710, 885 and 956 keV as the 2 ₂ ⁺ , 3 ₁ ⁺ and 0 ₂ ⁺ states, respectively. The data support the assumption of a non-axial deformation of¹⁰⁶Mo. A half-life of (1.02±0.05) s has been determined for theβ decay of¹⁰⁶Nb.