Hyperfine structure of ESR spectra as a probe for heisenberg exchange couplings in nitroxide triradicals serving as building blocks for molecule-based ferrimagnets

A study on electron spin resonance (ESR) spectroscopic determination of exchange interactions in organic oligoradicals is given. When the intramolecular exchange couplingJ between, unpaired electron spins in nitroxide-based oligoradicals falls within the order of 10 Oe (1 mK or 10^?3 cm^?1 forg=2), which is on the same order as the hyperfine couplingA of magnetic nuclei such as nitrogen atoms of nitroxide radicals, the magnitude ofJ can be determined from the hyperfine splitting pattern of ESR spectra in solutions. This range of the exchange couplingJ is not detectable in conventional magnetic susceptibility measurements. We demonstrate an application of hyperfine ESR spectroscopy as a probe for the exchange coupling to a series of organic oligoradicals, which the authors have recently developed as building blocks for molecule-based magnetic materials.     

A novel electronic-hyperfine perturbation in the C4Σ− state of VO

The hyperfine structure of the level N = 37, $\text{J = 38}\text{1}\text{2}$ in the C⁴Σ^?, v = 0 state of VO is anomalous as a result of an electronic perturbation. Because of the high nuclear spin of ⁵¹V ($\text{I =}\text{7}\text{2}$), the hyperfine pattern has a sufficient number of lines that it can be analyzed in detail just as if it were a rotational branch fragment containing an avoided crossing. It is shown how the coefficient of F(F + 1) in the hyperfine energy expression for the perturbing state and the perturbation matrix element can be obtained very accurately, though because the nature of the perturbing state is unknown it has not been possible to interpret the coefficient in terms of conventional hyperfine parameters in this case. The conditions for the appearance of perturbations of this type and the results to be obtained from them are discussed.     

Level crossing investigation of the hyperfine splitting in thez 6 P 7/2-level of EuI

By means of a level crossing experiment the hyperfine structure constants of thez ⁶ P _7/2-level of Eu have been determined. The results areA=-6.51(6) MHz andB= 131.2(1.0) MHz in the isotope¹⁵¹Eu andA=-2.84(3) MHz andB=327.5(1.5) MHz in the isotope¹⁵³Eu. Experimental data on the hyperfine splitting are available now for 11 of the 12 levels of the configuration 4f ⁷ (⁸S)6s 6p of EuI. These data are compared with the theoretical interpretation given by Bordarieret al. [1] which was based on only 7A-factors andB-factors. It is shown that the agreement between theory and experiment can be improved by taking into account configuration interactions.     

Nuclear hyperfine structure in the XΣ state of ZrC

Electronic band systems of zirconium monocarbide, ZrC, in the 16 000-19 000 cm⁻¹ region have been observed following the reaction of laser-ablated Zr atoms with methane under supersonic free-jet conditions. Rotational analyses of high-resolution spectra have shown that the ground state of ZrC is a ³Σ state, with r₀=1.8066 Å and an unexpectedly small spin-spin parameter, λ=0.5139 cm⁻¹. The spectra are dense because of the five naturally occurring isotopes of Zr. Four of these, with mass numbers 90, 92, 94, and 96, have I=0, but the fifth, ⁹¹Zr, present in 11.22% abundance, has I=5/2. Lines of ⁹¹ZrC can be assigned in some of the strongest bands, and are found to display sizeable hyperfine splittings, with widths of up to 0.2 cm⁻¹. Analysis shows that the largest hyperfine effects are in the ground state, where b=−0.03133±0.00015 cm⁻¹ and c=−0.00123±0.00037 cm⁻¹ (3σ error limits). The large Fermi contact parameter, b, indicates that an unpaired Zr 5sσ electron is present, which, taken together with the small value of λ, means that the ground state must be a ³Σ⁺ state, from the electron configuration (Zr 5sσ)¹ (C 2pσ)¹. Internal hyperfine perturbations occur between the F₁ and F₃ electron spin components of the ground state in the range N=2-4, producing extra lines in some of the branches; the perturbations are of the type ΔN=0, ΔJ=±2, and are a second-order effect arising because the F₁ (J=N+1) and F₃ (J=N−1) spin components both interact with the F₂ (J=N) component through ΔN=0, ΔJ=±1 matrix elements of the Fermi contact operator. Second-order perturbations of this type can only occur in states that are very close to case (b) coupling.     

The Lamb-dip spectrum of the J = 1 ← 0 transition of DF: Crossing resonances and hyperfine components

The Lamb-dip technique has been applied to the observation of the J = 1 ← 0 transition of DF: for the first time, the hyperfine structure due to D and F have been resolved by using microwave spectroscopy. The high accuracy of this technique allows us to provide hyperfine parameters that are in very good agreement with those obtained from molecular beam experiment. In addition, our frequencies together with the unresolved ones up to J″ value of 47 allow us to provide the most accurate ground state rotational constants of DF known at the moment. Furthermore, due to the presence of a relevant number of strong crossing resonances, the J = 1 ← 0 transition of DF can be considered an illustrative case to show how they modify the shape of Lamb-dip spectra.     

Mixing of the lowest-lying qqq configurations with J~P=1/2~- in different hyperfine interaction models

We investigate mixing of the lowest-lying qqq configurations with J~P=1/2~-caused by the hyperfine interactions between quarks mediated by Goldstone Boson Exchange,One Gluon Exchange,and both Goldstone Boson and One Gluon exchange,respectively.The first orbitally excited nucleon,Σ,ΛandΞstates are considered.Contributions of both the contact term and tensor term are taken into account.Our numerical results show that mixing of the studied configurations in the two employed hyperfine interaction models are very different.Therefore,the present results,which should affect the strong and electromagnetic decays of baryon resonances,may be used to examine the present employed hyperfine interaction models.     

A Mössbauer effect study of structural ordering in rapidly quenched Fe–Ga alloys

Samples of Fe_100−xGa_x (x=8.3, 17.9, 20.5 and 23.3) were prepared by rapid solidification from the melt using a single Cu roller. X-ray diffraction studies of all samples showed them to be single phase with the disordered BCC structure. No evidence of superlattice reflections from D0₃ ordering was observed for any of the samples. Room-temperature ⁵⁷Fe Mössbauer effect spectra indicated that all samples were ferromagnetically ordered. Spectra were fit to distributions of hyperfine fields. The x=8.3 sample showed a hyperfine field distribution that was single peaked and indicated a reasonably random distribution of local Fe environments. The x=17.9 and 20.5 samples showed hyperfine field distributions that were bimodal and indicated two distinct local Fe environments. The x=23.3 sample showed three distinct field components. It is suggested that the x=8.3, 17.9 and 20.5 alloys are primarily a disordered BCC phase. The x=8.3 alloy shows a small amount of short-range Ga–Ga pairing, while this short-range pairing is significantly greater in the x=17.9 and 20.5 alloys. The three field components in the x=23.3 alloy correspond well to the two sites associated with the D0₃ phase and a third component corresponding to a remaining L1₂ phase suggesting the presence of at least short-range D0₃ clustering in this alloy.     

The Lamb-dip spectrum of phosphine: The nuclear hyperfine structure due to hydrogen and phosphorus

For the first time, the hyperfine structure of the rotational J = 1 ← 0 (K = 0) and J = 2 ← 1 (K = 0, 1) transitions of phosphine has been resolved by using microwave spectroscopy. To this purpose, the Lamb-dip technique has been employed. In addition, the J = 3 ← 2 (K = 0, 1, 2) transition has been recorded at Doppler resolution. The present investigation allowed us to provide accurate values for most of the hyperfine constants as well as ground state rotational parameters.     

Hyperfine structure and isotope shift of highly excited barium-I states

High-resolution laser-spectroscopy measurements of hyperfine structure and isotope shifts were performed for the 6snd ¹ D ₂ sequence of Ba-I in the regionn=12–24. Stepwise laser excitations of a collimated atomic beam were used. A strong influence on the hyperfine structure is observed at the perturbation atn=14, caused by interaction with the 5d7d configuration. Whereas the isotope shift for the even isotopes stays essentially constant with increasingn, the odd isotopes exhibit a strong change, indicating hyperfine-induced shifts.     

The hyperfine structure and nuclear moments of some neutron-deficient as isotopes

The hyperfine structure of the¹³⁹La II line 5d ^{2 3} F→5d4f ³ F ₄ ⁰ atλ=579.8 nm has been investigated by means of collinear laser spectroscopy on a fast La⁺ beam. AmongΔF=0, ±1 hyperfine transitions,gDF=±2 transitions have been observed. An interpretation of theseΔF=±2 transitions as well as their relative line strengths is given by means of a three-quantum process.     

Resonanzstreuung von Licht in magnetischen und elektrischen Feldern zur Untersuchung der Hyperfeinstruktur des 7d 2 D 3/2-Terms im Thallium I-Spektrum

Observing the resonance fluorescence of the transition 7d ² D _3/2-6p ² P _1/2 (λ=2379 Å) in the Tl I-spectrum the level crossing technique with combined electric and magnetic fields was used to investigate the hyperfine structure and the Stark effect of the 7d ² D _3/2-state. For electric field strengthsE?25 kV/cm the Stark shifts are considerably greater than the hyperfine splitting. Therefore the crossing signals for the case of decoupled hyperfine structure could be detected. The following values of the magnetic hyperfine constantA and the Stark parameterβ were deduced: ¦A¦=55(1) Mc/sec·g _J /0.8, ¦β¦=0.20(4) Mc/sec/(kV/cm)²·g _J /0.8 andA/β>0. The widths of the signals yielded the mean lifetimeτ=2.7(5)·10^?8 sec· 0.8/g _J . Sign and values ofA andβ are discussed.     

Precision spectroscopy of metastable hydrogen and antihydrogen with a Lamb-shift polarimeter

A spinfilter, the most important component of a Lamb-shift polarimeter, can be used to produce a beam of metastable hydrogen (deuterium) atoms in one hyperfine state (α1, α2 and together with the Sona transition β3). As function of a magnetic field separated transitions between the 2S _1/2 metastable hyperfine states seem to be observable as well as single transitions into the short-lived 2P _1/2 and 2P _3/2 states. The Breit-Rabi diagrams for these states can be measured with good precision. Furthermore, the hyperfine splittings and the Lamb shift can be observed as well. Application of this method to anti-hydrogen atoms are suggested.     

Facteur de landé du niveau (6s26p 7s) 3P1 du plomb et constante de structure hyperfine de l'isotope 207Pb dans ce niveau

The Landé factor g_J of the (6s² 6p 7s)( ³P₁ level of the even isotopes of lead has been measured by Fabry-Pérot interferometry. The result is: g_J=1.3500(4). The agreement with the previously measured hyperfine splitting of this level for the isotope ²⁰⁷Pb and with the level crossing results is good when small corrections (nuclear Zeeman interaction, second-order hyperfine and Zeeman corrections) are taken into account. The corrected hyperfine dipole coupling constant for this level of ²⁰⁷Pb is: A=293.60(13) mK.     

Mössbauer study of Zn effect on BCC iron in metastable Fe−Zn alloys

In metastable sputtered Fe_1?y Zn _y alloys, the bcc Fe-rich α phase, alone or mixed with another phase, was found in the concentration range 0<y<0.6. This Fe_1?x Zn _x bcc phase can contain substituted Zn atoms up tox=0.43. Analysis of Mössbauer spectra by a binomial distribution law, taking into account the first and second neighbours, is consistent with an homogeneous distribution of Zn in this phase. The correlations between hyperfine parameters have been determined as a function ofx. The deduced local hyperfine coupling constants are equal to 922 kOe/s-el and to 1435 kOe/s-el for a Zn atom located respectively at the first or second neighbour shell.     

Nuclear magnetic resonance on oriented194Ir (T 1/2=19.4 h) in Fe and Ni

The hyperfine interaction of¹⁹⁴Ir (j ^π =1^?;T _1/2=19.4 h) in Fe and Ni has been investigated with the technique of nuclear magnetic resonance on oriented nuclei. For both systems the electronic-orbital-momentum induced electric quadrupole splitting could be resolved. The magnetic and electric hyperfine splitting frequencies,v _M =¦gμ _N ^B _HF/h¦ andv _Q =e ² qQ/h, respectively, were measured as:¹⁹⁴IrFe:v _m =408.54 (23) MHz;v _q =?2.47(20) MHz;¹⁹⁴IrNi:v _M =135.24(5) MHz;v _q =?1.23 (3) MHz. Taking into account a 3% uncertainty arising from hyperfine anomalies theg-factor is deduced as ¦g¦=0.39 (1). The electric quadrupole moment,Q=+0.352 (18)b, is slightly smaller than expected from the known systematics of deformation parameters in this mass region.     

Nuclear magnetic resonance on oriented192Ir in Fe and Ni

The hyperfine interaction of¹⁹²Ir nuclei as dilute impurities in Fe and Ni has been investigated with NMR on oriented nuclei. With the use of highly dilute and pure alloys the line widths could be reduced so far that the quadrupole splitting of¹⁹²IrFe and¹⁹²IrNi could be resolved. Taking hyperfine anomalies into account the ground state nuclear moments of¹⁹²Ir are deduced as |μ|=1.924(10)μ _N andQ=2.36(ll) b. The hyperfine field of IrNi was investigated as a function of the Ir concentrationc between 0.01 at % and 5 at %. The dependence ofH _HF onc was found to be significantly smaller than that reported from Mössbauer effect measurements. Forc=0.01 at %H _HF=?454.7(2.3)kG is deduced. The resonance shift with an external magnetic field has been studied precisely, yieldingK=0.012(23) andK=0.026(12) for the Knight-shift of¹⁹²Ir in Fe and Ni, respectively.     

Doppler-limited rotational spectrum of the NH radical in the 2 THz region

The Doppler-limited rotational spectrum of the NH radical in its electronic (X) and vibrational ground state has been measured using the frequency stabilized Cologne side-band spectrometer in the frequency region near 2 THz. The nitrogen ¹⁴N nuclear hyperfine patterns have been observed accompanying the resolved fine (J^′←J″) structure of the N=2←1 rotational transition. The observed peak frequencies were analyzed in detail together with the previously measured hyperfine frequencies of the N=1←0 rotational transition and with combination differences obtained from the high-resolution electronic spectra to derive precise rotational, centrifugal distortion, fine, and hyperfine parameters. In the numerical analysis the essential attention has been paid to partly resolved and unresolved hyperfine structures. The peak positions of the partly or fully overlapped lines were analyzed with the help of a profile simulation with estimated half-widths and calculated relative intensities and in this manner the least square fit of the unresolved and partly resolved lines was significantly improved. The NH radical is an extremely important species in nitrogen chemical reaction networks in the interstellar medium and atmospheric chemistry.     

Mössbauer effect study of hyperfine interactions in145Nd

The magnetic hyperfine splitting of the 72.5 keV γ rays of¹⁴⁵Nd was investigated in intermetallic compounds of Nd and in the paramagnetic salts Nd _x Y _1-x Cl₃·6H₂O (withx=0.02 andx=0.05) at 4.2 K. With the magnetic hyperfine tensorA of Nd_0.01Y_0.99Cl₃·6H₂O known from EPR spectroscopy, the analysis of the unresolved magnetic hyperfine spectra yieldsI _e =5/2 for the spin of the 72.5 keV state, in contradiction to a previous result. The multipolarity of the 72.5 keV γ transition was found to be essentiallyM1 with δ²=0.010±0.014, and the magnetic moment of the 72.5 keV state was determined as μ(5/2)=?0.319±0.004 nm. For various divalent and trivalent Nd compounds as well as for metallic Nd the isomer shift IS of the 72.5 keV γ line was measured. A value for the change of the mean square nuclear charge radius during the 72.5 keV γ transition of Δ〈r ²〉=+(1.9±0.9)·10^?3fm² was deduced using electron density differences from free-ion Hartree-Fock calculations.     

Mössbauer studies in amorphous Fe80−x−y Ni x Mn y B12Si8 alloys

Room temperature Mössbauer studies have been carried out on amorphous Fe_80?x?y Ni _x Mn _y B₁₂Si₈ (x=35, 40, 45, 50 and 0≤y≤1). Thex=40 and 45 samples, showed an increase in the average hyperfine field, wheny increased from 0.0 to 0.2 at% in the former and 0.0 to 0.5 at% in the latter. The hyperfine field decreased fory=1.0. This is similar to the results of the magnetic moment on these samples, published earlier.