The phosphorescent triplet state of p-xylene in an isotopically mixed crystal at 1·2K: an investigation by E.S.R. and MIDP

The phosphorescence spectrum of p-xylene-h ₁₀ in a p-xylene-d ₁₀ host is first presented. Secondly we report E.S.R. experiments performed on p-xylene-α,α′-d ₆ in p-xylene-d ₁₀; from an analysis of the orientations of the principal axes in combination with the crystal structure and of the hyperfine splittings it is concluded that the in-plane principal axes of the zfs tensor make an angle of 68° with the molecular axes. Thirdly we discuss Microwave-Induced Delayed Phosphorescence (MIDP) experiments on p-xylene-h ₁₀ in p-xylene-d ₁₀ in which the relative radiative rate constants for decay from the zero-field spin components of the triplet state to single vibronic bands of the ground state have been obtained.

The results of the MIDP and E.S.R. measurements are shown to be mutually consistent in terms of a model in which the effect of the crystal field and the methyl substituents on the pseudo-Jahn-Teller unstable electronic structure of the triplet state of benzene is described.     

Mössbauer spectrum of an ensemble of57Fe nuclei interacting with radiation fields coupling the Zeeman sublevels of the nuclear excited 3/2 state

We have introduced the concept dressed nucleus in order to describe the interaction of a nucleus (in a static magnetic field) with a radiation field havingn photons of a certain mode. The idea is to consider the global system as one quantum system in the Schrödinger representation. The number of eigenvalues of the Hamiltonian of the global system is (2I+1)², withI the spin of the free nuclear state. Taking into account the form of the corresponding eigenvectors and the relevant selection rules, the total number of -transitions (for the nuclear transition 3/2^- 1/2^-) is 24. If a Mössbauer effect experiment is set up with a single-line absorber, the source being an ensemble of dressed nuclei, we would expect a spectrum showing 24 lines, whose relative positions and intensities are calculated.     

Relaxation of the magnetic state of a ferromagnetic–superconducting layered structure

We have proposed a real-time method of neutron reflectometry. The magnetic state of the Ta/V/FM/Nb/Si ferromagnetic–superconducting system has been analyzed. Relaxation of the inhomogeneous magnetic state with a characteristic time of several hours, which depends on the magnetic field magnitude and temperature, has been observed. The relaxation of the domain structure has changed upon a transition of the V and Nb layers to the superconducting state. It has been concluded that real-time reflectometry data for polarized neutrons are important for determining the origin of magnetism in ferromagnetic–superconducting layered structures.     

Calculation of the elastic scattering properties for cold and ultracold 39K atoms in a triplet state

The elastic scattering properties for collisions between cold and ultracold 39K atoms in a triplet state are investigated. Based on the recent theoretical and experimental results, the improved hybrid potential is presented for a triplet α3∑u^＋ ground state of K2. Our calculated value of the s-wave scattering length a by using the Numerov method for the triplet state is 79.578α0 and found to be in good agreement with the previous ones. The numbers of bound states are supported by the molecular potential. Pronounced shape resonances appear for the l = 3 partial waves for the α3∑u^＋ state. Furthermore, the s-wave scattering cross section, the total cross section and energy positions of shape resonances for the α3∑u^＋ state are calculated.     

First exclusive measurements of the K − pp state populated in the pp → K + Λp reaction at 2.85 GeV

We have analyzed data of the DISTO experiment on the exclusive pp → K ^?+? Λp process at T _p ?=?2.85 GeV to search for a K ^??? pp  (?≡?X) nuclear bound state to be formed in the pp → K ^?+??+?X reaction. The deviation spectra of the K ^?+? missing-mass ΔM (K ^?+?) and Λp invariant-mass M(Λp) with selection of large-angle proton emission revealed a structure with M _X ?=?2265 ±2 MeV/c ² and Γ _X ?=?118 ±8 MeV.     

Optically detected EPR effect in the ã3 Au triplet state of the oxalylfluoride molecule excited to the 413, 423 and 431 rotational levels of the 00(Ã1 Au ) vibronic state

In the present study, resolved OD EPR spectra were measured for the 4₃₁, 4₂₃, and 4₁₃ levels of the ù A_u 0⁰ vibronic state. Values of the fine and hyperfine constants were estimated from an analysis of these spectra for the triplet rotational levels, coupled by the intramolecular interactions with the singlet levels studied. It was shown that the microwave power dependence differs significantly for different lines of the OD EPR spectrum. This difference can be explained by a model where the microwave field saturation effect is observed for different OD EPR lines at different power values of the microwave field. The decay profile can be fitted by a biexponential function in the presence of both magnetic and microwave fields. The observed data were analysed using the electron and nuclear spin decoupling mechanism in the limit of low level density.     

The effect of the hydrogen fluoride chain on the aromaticity of C6H6 in the C6H6···(HF)1–4 complexes

The effect of the hydrogen fluoride chain ((HF)_n) on the aromaticity and π character of C–C bonds of C₆H₆ in the C₆H₆···(HF)_n (n = 1–4) complexes were investigated using density functional theory employing RM05 functional. It was found that the binding energy between C₆H₆ and different (HF)_n chains showed a maximum at n = 3 (C₆H₆···(HF)₃). Also, the π–hydrogen interaction (πHI) and the bifurcated fluorine interaction (BFI) increased and decreased the π character of the C–C bond of C₆H₆, respectively. In addition, the change of aromaticity of the C₆H₆ due to the interaction with the HF chains was also studied using three different aspects such as aromatic fluctuation index (FLU), average two centre index (ATI) and proton nuclear magnetic resonance (HNMR) spectrum. The most change in the aromaticity happens when the C₆H₆ interacts with (HF)₃ chain. The variation of aromaticity with the binding energy and the summation of two-body terms were investigated and very good linear correlations were observed.     

Cross sections of the interactions of4He nuclei with protons at 8·6 and 13·6 GeV/c

⁴He-p collisions at two values of⁴He momenta-8·6 GeV/c and 13·6 GeV/c — have been studied using the one-metre JINR hydrogen bubble chamber. Total, elastic and topological cross sections have been measured. The results are in agreement with other published data. The elastic differential cross section was compared with the predictions of the Glauber model formalism.Dedicated to Academician Václav Votruba on ths occasion of his eightieth birthday.We would like to thank Mrs. M. Stehlíková for drawing the figures.     

Twisting of α-quartz tetrahedra at pressures near the transition to the amorphous state

It is found that the main contribution to the distortion of α-quartz tetrahedra at high pressures is their twisting. It is shown that torsional vibrational modes lead to an instability that gives rise to amorphization of the structure. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 6, 431–435 (25 March 1999)     

The description of the Kπ = 1+ isovector M1 state within a boson expansion formalism

A nuclear system of Z protons and N neutrons moving in an anisotropic potential well and interacting among themselves through an isoscalar plus an isovector quadrupole-quadrupole interaction is treated within a boson expansion formalism. The expansion is performed in terms of the particle-hole RPA bosons. Application refers to ¹⁵⁶Gd. Appreciable corrections to the RPA results concerning both the energies and the B(M1↑) values are obtained. The higher RPA corrections destroy the fragmentation of the RPA-M1 strength and most of the collectivity is concentrated in one state.     

The photodetachment spectrum of OHF−: the influence of vibration at a transition state

New ab initio potential energy functions for collinear OHF^? and OHF have been used with time-dependent wavepacket studies in a simulation of the photodetachment spectrum of the OHF^? anion. Franck—Condon excitation of OHF^? lies within the transition state region for the bimolecular reaction F + OH ? O + HF on the lowest triplet surface. The branching ratios for fragmentation of the excited OHF are such that the peaks in this spectrum may each be correlated with dissociation to a single vibrational state of the O + HF(v) or OH(v) + F products. The possible influence of vibrational excitation of the anion has been explored also. This is predicted to lead to marked changes in the spectra. Experimental observations of such spectra could be used in refinement of the potential as could an experiment in which the electron kinetic energy is detected in coincidence with the vibrational states of the molecular products or with the kinetic energy of the atomic products. The calculations revealed a number of metastable resonances on the OHF surface, although these are all at higher energies than are relevant to the photodetachment spectrum from the ground state anion.     

Potential of the A 1Σ u + state of He2

The potential of the lowest excited singlet state of He₂ is calculated. The best function includes 209 configurations constructed from 10 σ basis orbitals. Excellent agreement with experimental quantities depending on the shape of the potential near the minimum (equilibrium interatomic separation, vibrational and rotational constants for the lower vibration levels) is obtained. The dissociation energy is 18 600 cm^-1, compared to the experimental 19 910±50 cm^-1. Agreement is not as good for the highest vibrational levels.     

ENDOR amplitudes of triplet state molecules: II. Orientational dependence of the νp frequency line and S-T0 mixing

The specific ENDOR line at the free Larmor frequency ν_p in the low temperature spectra of triplet state molecules is caused by degenerate NMR transitions within theM _s=0 zero-level (ZL) electron spin manifold. This ZL line was found to be orientationally dependent for the diradical complex Zn(3,6-di-tert-butyl-o-semiquinone)₂Zn(DBSQ)₂: the ZL line dominates the ENDOR spectrum if it is detected at the perpendicular canonical components of the EPR spectrum, and vanishes if the complex is oriented with its ZFSz-axis parallel to the direction of the magnetic field, i.e., if detected at the parallel canonical EPR components. This effect is shown to result from the interaction between nuclear spin substates of the S and T₀ manifolds, their levels being close to each other for the Zn(DBSQ)₂ complex. Such an interaction mixes the states and shifts energy levels. Consequently, it cancels the degeneracy of the nuclear substates within the ZL manifold and reduces the rate of nuclear flip-flop relaxation. This specific relaxation mechanism has been shown to substantially affect the amplitude of the ZL line (Doubinskii A.A., Lebedev Ya.S., Möbius K.: Appl. Magn. Reson.13, 439 (1997)). The nuclear flip-flop relaxation effect is expected to be orientationally dependent since the S-T_o separation depends upon the orientation of the diradical with respect to the external magnetic field.     

Excitation and concentration dependence of the luminescence of chrysene at 77°K

For low concentrations of chrysene in rigid glass matrices at 77°K, the intersystem crossing ratio is found to be independent of wavelength of excitation. Fluorescence decay times of perdeuterated and undeuterated chrysene indicate only a slight isotope effect on the intersystem crossing rate constant. At higher concentrations a new emission is observed and attributed to microcrystalline chrysene.