E.S.R. study of the conformational kinetics of a biradical

Intramolecular motion in the biradical N,N'-bis(2,2,6,6-tetramethyl-1-oxyl-4-piperidinyl)ethylenediamine which contains two ionizable amine groups has been studied by E.S.R. spectroscopy. The line-shapes of the spectra as a function of pH and temperature were analysed by density matrix methods to give values for rates and free-energies of activation.     

Calculation of the E.S.R. spectrum shape of the dynamic biradical system

The E.S.R. spectrum shape of a dynamic biradical system is calculated by means of the density spin-matrix formalism. The biradical is treated as a system which has two conformations characterized by the different values of the exchange integrals J=J ₁ and J=J ₂ and the lifetimes τ₁ and τ₂ respectively. The influence of both the rate and the strength of exchange interactions on the shape of the spectrum is discussed. Criteria to distinguish the spectra of the cases of both slow and fast exchange are discussed.     

Rapid computer simulation of E.S.R. spectra

A fast computer algorithm is presented which permits simulation of the effects of rotational diffusion, electron and nuclear relaxation, microwave power, and modulation frequency upon saturation transfer (passage) E.S.R. spectra. Comparison of theoretical and experimental spectra for nitroxide spin-labelled biomolecules suggests that while the dependence of electron spin-lattice relaxation time upon rotational correlation time is weak, the variation of the ratio of the electron to nuclear spin-lattice relaxation times is significant and consideration of strong nuclear relaxation is necessary for the simulation of spectra characterized by correlation times near the reciprocal of the nitrogen nuclear resonance frequency.     

The McConnell equation for E.S.R. spectra of symmetrical diazanaphthalenes

Electron spin resonance spectra of the six symmetrical diazanaphthalene anions in N,N-dimethylformamide have been measured. The anions were generated within the microwave cavity by electro-reduction of the parent compound. The McConnell equation a _H = Q _CC ^H ρ C has been tested for the diazanaphthalenes with ρ C values calculated by the Hückel method and by the Pariser-Parr-Pople S.C.F. method with variable resonance integrals.     

E.S.R. spectra of X-irradiated methylene diphosphonic acid

X-irradiation of single crystals of methylene diphosphonic acid gives rise to E.S.R. spectra which have been assigned to (OH)₂(O)P-?H₂ and

The former species is the more abundant of the two and the methylene group undergoes rapid re-orientation about a two-fold axis at room temperature but is stationary at 77 K. The ¹H and ³¹P coupling constants in this radical are very similar to those in Ph₃P⁺CH₂, and support the previous conclusions [1] that there is little delocalization of the unpaired electron to the phosphorus atom.     

E.S.R. spectra and hyperfine structure of symmetric trinuclear clusters

The E.S.R. spectrum hyperfine structure of trigonal trinuclear exchange clusters with half-integral spins is presented. In the case of antiferromagnetic exchange coupling, the ground state with the total spin S = ½ is four-fold degenerate. The Heisenberg-Dirac-Van Vleck model is shown to be incorrect for the problem of hyperfine interactions. The theory of E.S.R. hyperfine structure presented here arises from the group-theoretical analysis of exchange multiplets. By means of irreducible tensor methods the hyperfine interaction effective hamiltonian is constructed. The angular and field dependence of the hyperfine structure is investigated.     

Highly resolved electronic absorption and luminescence spectra of some phenanthrolines in Shpolskii matrices: Part II. Fluorescence and S1←S0 absorption spectra

Highly resolved fluorescence and S₁←S₀ absorption spectra of some phenanthrolines in n-alkane matrices were obtained at 77 K. The vibrational analysis of the spectra was carried out. Mirror symmetry distortions of the fluorescence and absorption spectra were attributed to vibronic coupling between ¹(π, π¹) states. It was shown that vibronic mixing of S₁(π, π¹) and S₂(π, π¹) states occurs in phenanthroline molecules with S₁-S₂ energy gap not exceeding 3000 cm^-1 (i.e., 4,7-, 1,7- and 1,10-Phen), whereas in other phenanthrolines the coupling of S₁ and S₃(π, π¹) plays a dominant role. Fluorescence quantum yields of phenanthroline liquid solutions were measured. Changes of luminescence efficiencies due to the change of the polarity of the media point to a weak coupling of the lowest ¹(π, π¹) and ¹(n, π¹) states.     

Calculation of the E.S.R. spectrum of a dynamic biradical system with more than two conformations

The E.S.R. spectrum of a biradical with any number of conformations is calculated. It is shown that in some cases the interpretation of the E.S.R. spectra of such biradicals can be carried out in terms of groups of the conformations with fast exchange inside the groups. It is shown also that in the case of fast exchange the averaging of describing spectrum parameters is performed over concentrations of the exchanging conformations but not over their lifetimes, as it was suggested earlier. A detailed treatment of the spectra of biradicals with three conformations is carried out, and the possibilities of the analysis of experimental spectra of long-chain nitroxide biradicals are shown.     

E.S.R. spectra of diboranyl radicals in the solid states

E.S.R. Spectra of the radicals produced from the γ-irradiated diborane (6) in polycrystal or single crystal have been investigated. From the analysis of the results of the single crystal, the radical was identified as neutral diboranyl, ·B₂H₅, produced by extracting one of the two bridging hydrogen atoms of diborane. The major portion of the spin density on the radical is equally shared by the two boron atoms, a considerable portion exists on the bridging hydrogen atom, and a small portion with negative sign on the four terminal hydrogens. The orbitals of the unpaired electron on the two borons are in the same plane at an angle of 73°. These results are in good agreement with those from INDO calculation for the radicals. The structure of the radical is discussed in comparison with some other radicals having a similar structure.     

Evidence for slow exchange in E.S.R. spectra of nitroxide biradicals

Force constants have been calculated for H₂NF and HNF₂ from ab initio Hartree-Fock wavefunctions by the force method, using 7s3p/1 gaussian basis sets. The force field of HNF₂, obtained from a combination of the theoretical results with the experimental frequencies, can be considered as the most reliable one at present. Previous force fields are discussed critically. From a full optimization the predicted geometry of H₂NF is: NF = 1·399 Å, NH = 1·018 Å, HNF = 102·9° and HNH = 105·9°.     

Dynamic frequency shift in the E.S.R. spectra of transition metal ions

The factors which determine the electron spin resonance lineshapes and shifts of transition metal complexes in solution are discussed. It is shown that for ions with S > ½ the dynamic frequency shift may have pronounced effects on the E.S.R. lineshapes, and experimental evidence for this effect in complexes of Cr³⁺, Fe³⁺ and Gd³⁺ is presented. A quantitative interpretation of these spectra in terms of a relaxation mechanism due to fluctuation of the quadratic zero field splitting interaction is given.     

The E.S.R. spectrum of the tropolonyl radical

The many-body diagrammatic Rayleigh-Schrödinger perturbation theory (RSPT) is used for the calculation of ionization potentials of open-shell systems with one unpaired electron. This theoretical approach is tested on the simple examples of NO₂ and NF₂ molecules described by the INDO semi-empirical hamiltonian. The first- and second-order results are presented.     

Interpretation of S-state ion E.P.R. spectra

Although a considerable body of data exists on the parametrization of the ground-state splittings of S-state ions in crystals, relatively little progress has been made in obtaining a quantitative understanding of the mechanisms which determine these parameters. In the course of summarizing our present understanding, we emphasize the need for making planned experiments explicitly aimed at testing theoretical models, such as those proposed in this article. The variable frequency E.P.R. technique is described in some detail, as it has proved to be particularly useful in this respect.     

The E.S.R. spectrum of irradiated ammonium hypophosphite

Electron spin resonance spectra of irradiated crystals of ammonium hypophosphite (NH₄)⁺(H₂PO₂)^- indicate that the ionic radical H[Pdot]O₂ ^- is initially formed. The hyperfine interaction tensor of the phosphorus nucleus has the principal values 1698, 1228 and 1228 Mc/s. Interaction with the proton gives rise to an almost isotropic hyperfine coupling of 230 Mc/s. These results indicate that the species H[Pdot]O₂ ^- is irregular tetrahedral in shape, the unpaired electron occupying a hybrid σ orbital centred on the phosphorus nucleus.

There is evidence that the radical H[Pdot]O₂ ^- reacts with an adjacent H₂PO₂ ^- ion forming the species O₂[Pdot]-PHO₂ ⁼. The principal values of the hyperfine interaction tensors of the two phosphorus nuclei are 1365, 944, 921 Mc/s and 527, 362, 359 Mc/s respectively. The proton has an isotropic hyperfine coupling of 90 Mc/s. The spectra of irradiated deuterated crystals confirmed this analysis.     

E.S.R. spectra of SiF3 radicals produced in a single crystal of SiF4

E.S.R. spectra of a γ-irradiated single crystal of SiF₄ were investigated. The spectra observed were attributed to SiF₃ radicals having ²⁸Si (I=0) and ²⁹Si (I=1/2) atoms. From the angular dependence of the spectral lines on rotation of the single crystal, hyperfine tensors were determined for three fluorine atoms and the ²⁹Si atom of the SiF₃ radical. The three fluorine atoms in the radical are equivalent, whereas the directions of their hyperfine tensors are different from one another owing to the pyramidal structure of the radical. In addition to the hyperfine analysis, the analysis of the superhyperfine structure due to neighbouring fluorine atoms gave information on the orientation of the radicals in the crystal and the mechanism of radical formation. The structure of the radical is discussed in comparison with that of the CF₃ radical.     

E.S.R. spectra of PF4 radicals produced in a single crystal of PF3

E.S.R. spectra of PF₄ radicals were investigated with single crystals of PF₃ made at a low temperature and irradiated with γ-rays. The angular dependence of the spectral lines was satisfactorily analysed in terms of the second-order equations for large couplings of one ³¹P nucleus and two magnetically equivalent ¹⁹F nuclei and of the first-order equation for two ¹⁹F nuclei with small couplings. We conclude that the two magnetically equivalent fluorine nuclei occupy the axial positions of the trigonal bipyramidal structure of the PF₄ radical and the other two fluorine nuclei are in the equatorial positions. Furthermore, the unpaired electron of the PF₄ radical was shown to occupy an orbital consisting mainly of the 2p orbital of each of the two axial fluorine atoms along the F-P-F axis and the 3s and 3p orbitals, directed towards the vacant equatorial position of the central phosphorus atom. The orbital of the unpaired electron can be reasonably represented as a Rundle three-centre non-bonding orbital. The results obtained for the PF₄ radicals not only strongly support the results given for POCl₃ ^- radicals, but also allow us to discuss the electronic structure of phosphoranyl radicals in more detail.     

Growth and electronic absorption spectra of crystalline guanine hydrochloride dihydrate

Czechoslovak Journal of Physics -