Measurement of Δ1J(199Hg, 31P) in [HgPCy3(OAc)2]2 and relativistic ZORA DFT investigations of mercury–phosphorus coupling tensors

Using ³¹P solid-state NMR spectroscopy, anisotropy in the indirect ¹⁹⁹Hg-³¹P spin–spin coupling tensor (ΔJ) for powdered [HgPCy₃(OAc)₂]₂ (1) has been measured as 4700±300 Hz. Zeroth-order regular approximation (ZORA) density functional theory (DFT) calculations, including scalar and spin-orbit relativistic effects, performed on 1 and a series of other related compounds show that ΔJ(¹⁹⁹Hg, ³¹P) arises entirely from the ZORA Fermi-contact–spin-dipolar cross term. The calculations validate assumptions made in the spectral analysis of 1 and in previous determinations of ΔJ in powder samples, namely that J is axially symmetric and shares its principal axis system with the direct dipolar coupling tensor (D). Agreement between experiment and theory for various ¹⁹⁹Hg, ³¹P spin–spin coupling anisotropies is reasonable; however, experimental values of ¹J(¹⁹⁹Hg, ³¹P)_iso are significantly underestimated by the calculations. The most important improvements in the agreement were obtained as a result of including more of the crystal lattice in the model used for the calculations, e.g., a change of 43% was noted for ¹J(¹⁹⁹Hg, ³¹P)_iso in [HgPPh₃(NO₃)₂]₂ depending on whether the two or three nearest nitrate ions are included in the model. Finally, we have written a computer program to simulate the effects of non-axial symmetry in J and of non-coincidence of the J and D on powder NMR spectra. Simulations clearly show that both of these effects have a pronounced impact on the ³¹P NMR spectrum of ¹⁹⁹Hg–³¹P spin pairs, suggesting that the effects should be observable experimentally if a suitable compound can be identified.     

The magnetic moments and halflives of the 5/2− states in199Hg and197Hg and the discrepancies in the experimental hyperfine fields at Hg in Fe

The Larmor-precession frequencies for¹⁹⁷Hg in Fe have been determined to beω _L = 1291 ±25 MHz at 293 K andω _L = 1334±25 MHz at 105 K. For¹⁹⁹Hg in Feω _L =1372±50 MHz has been measured at 293 K. The half-lives of the 5/2^? states in¹⁹⁷Hg and¹⁹⁹Hg have been remeasured asT _1/2(¹⁹⁷Hg)=8.1±0.16 nsec andT _1/2(¹⁹⁹Hg)=2.45±0.05 ns, respectively. The magnetic moment of the 5/2^? 158keV state in¹⁹⁹Hg was redetermined by the integral perturbed angular correlation method in an external magnetic field of 47kG asμ(5/2 ^? ) = 0.905±0.091 nm. With this new value consistency for the magnetic hyperfine fields at Hg in Fe measured with the TDPAC-method and with the NMR/ON-method is obtained. This fact is used to determine theg-factors of the 5/2^? states in¹⁹⁷Hg and¹⁹⁹Hg more precisely fromω _L -values given above:g(¹⁹⁷Hg)=0.342(6);g(¹⁹⁹Hg)=0.352(13). The magnetic moments of the first excited 2⁺ states in^198–204Hg isotopes which rely on calibrations with the¹⁹⁹Hg-g-factor, are revised.     

Experimental study of 199Hg spin anti-relaxation coatings

We report on a comparison of spin relaxation rates in a ¹⁹⁹Hg magnetometer using different wall coatings. A compact mercury magnetometer was built for this purpose. Glass cells coated with fluorinated materials show longer spin coherence times than if coated with their hydrogenated homologues. The longest spin relaxation time of the mercury vapor was measured with a fluorinated paraffin wall coating.     

Theoretical study of hyperfine coupling constants and electron spin g factors for X2Σ+ diatomics from Groups 1 and 2

The ESR parameters of the cations Be⁺ ₂, Mg⁺ ₂, Ca⁺ ₂, BeMg⁺, BeCa⁺, MgCa⁺ and the mixed radicals ZBe, ZMg, ZCa (Z = Li, Na, K), all having a X ²Σ⁺ _u(1σ² _g1σ_u)/X ²Σ⁺(1σ²2σ) ground state, have been studied theoretically. The A _iso and A _dip constants have been calculated with UHF, CISD, MP2, B3LYP, PW91PW91 wavefunctions, and 6–311+G(2df) basis sets. The electron spin g factors (magnetic moment μ_s) have been evaluated from correlated (MRDCI) wavefunctions, using a Hamiltonian based on Breit-Pauli theory with perturbation expansions up to second order, and 6–311 + G(2d) basis sets. As expected for s-rich radicals, the hyperfine spectra are governed by the A _iso terms. Both Δg∥ and Δg⊥ values are negative, but Δg∥ lies close to zero. For Δg⊥, the coupling with 1 ²Π_(u) dominates the sum-over-states expansions. Although the singly occupied MOs (SOMO) are mostly of s character, the |Δg⊥| are relatively large, up to 5200 ppm for cationic, and up to 7850 ppm for neutral radicals. These large values are caused by low excitation energies and high magnetic transition moments, the latter due to the fact that the σ?(s-s) SOMO has the same nodal properties as a pσ orbital. Of the radicals considered here, an ESR spectrum is available only for Mg⁺ ₂. Our theoretical A _iso of ?287 MHz reproduces well the matrix result (-291 MHz). Calculated values of ?10 ppm for Δg∥ and of ?1280 ppm for Δg⊥ give an average 〈Δg〉 = ?860 ppm that lies within the experimental range of ?600(±300) ppm in Ne, and of ?1300(±500) ppm in Ar matrices.     

Study of orientation transfer by collisions of the second kind between 198Hg and 199Hg atoms

A double resonance experiment is used to detect the collisional transfer of orientation from an optically oriented ¹⁹⁸Hg (6³P₁) atom to the hyperfine levels $\text{(6}{}^3\text{P}{}_1\text{; F =}\text{1}\text{2}\text{, F =}\text{3}\text{2}\text{)}$ of a ¹⁹⁹Hg atom. The reaction of transfer is assumed to be ¹⁹⁸Hg (6³P₁) + ¹⁹⁹Hg (6¹S₀) → ¹⁹⁸Hg (6¹S₀) + ¹⁹⁹Hg (6³P₁).The theory of such a process is summarized, the experimental set-up described and the double resonance signals compared with those predicted by the theory.     

Investigation by EPR and ENDOR spectroscopy of the novel 4Fe ferredoxin fromPyrococcus furiosus

The hyperthermophilic archaeonPyrococcus furiosus contains a four-Fe ferredoxin (Pf- Fd) that differs from most other 4Fe-Fd’s in that its [Fe₄S₄] cluster is anchored to protein by only three cysteinyl residues.Pf- Fd also is of interest because in its reduced form, [Fe₄S₄]⁺, the cluster exhibits bothS = 1/2 andS = 3/2 spin states. Addition of excess cyanide ion converts the cluster exclusively to anS = 1/2 state (g₁ = 2.09, g₂ = 1.95, g₃ = 1.92), however dialysis restores the EPR signal of native reduced protein indicating that the cluster is not irreversibly altered by cyanide. Both the native protein and protein in the presence of excess cyanide ion (Pf- Fd 4Fe-CN) were investigated here using the techniques of electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. In particular,Pf- Fd 4Fe-CN was investigated using¹³CN^? and C¹⁵N^? ligands.¹³C and¹⁵N ENDOR indicated that a single cyanide ion bound directly, with the cluster showing an unusually small contact interaction (a_iso(¹³C)～ ?3 MHz, a_iso(¹⁵N) ～ 0). This is in contrast to cyanide bound to monomeric low-spin Fe(III)-containing proteins such as transferrin and myoglobin, for which the¹³C hyperfine coupling has a large isotropic component (a_iso(¹³C) ≈ ?30 MHz). This small contact interaction is not due to low spin density of Fe, as⁵⁷Fe ENDOR of the singly and triply labeledPf- Fd 4FeCN isotopologs, [⁵⁷FeFe₃S₄]⁺ and [Fe⁵⁷Fe₃S₄]⁺, show hyperfine coupling characteristic for [Fe₄S₄]⁺ clusters, particularly for the Fe to which cyanide binds. Thus, the low spin density on¹³C is not due to low spin density on the Fe ion to which it binds. Further theoretical work is needed to explain the contrast between the strong electronic effect of cyanide ion binding with the low spin density on the ligand.     

199Hg and63,65Cu NMR studies of mercury based high-T c superconductors

Hg-oxide ceramic high temperature superconductors were studied by¹⁹⁹Hg and^63,65Cu NMR spectroscopy. Room temperature spectra, spin-spin and spin-lattice relaxation times of samples with different superconducting transition temperatures are presented. A spin-lattice relaxation time ofT ₁=35 msec and a spin-spin relaxation time ofT ₂=1.6 msec were found for the¹⁹⁹Hg NMR. All samples exhibit similar characteristic powder spectra caused by an axially symmetric¹⁹⁹Hg spin interaction. The isotropic value and the anisotropy of the tensor relative to solid HgCl₂ as a standard substance is estimated. Furthermore, results of^63,65Cu NMR measurements at a temperature of 4.2 K which exhibit a typical powder line shape (forI=3/2) are presented.     

Nuclear quadrupole interaction of119mHg in mercury(I) and mercury(II) halides

The nuclear quadrupole interactions of^199mHg in the mercury(I) and mercury(II) halides with Cl, Br, I were determined by time differential perturbed angular correlation. The quadrupole moment of theI=5/2 state in¹⁹⁹Hg was redetermined to beQ _5/2=0.674(77) b. The nuclear quadrupole interaction in both mercurous and mercuric halides scales with the electronegativity. Electric field gradients at mercury and halogen sites were calculated by a full-potential linearized augmented plane wave method (WIEN code) and were found in good agreement with experiment. In some cases a total energy minimization for internal parameters was carried out and found to be essential.     

199Hg Mössbauer measurements on mercury alloys and Hg-fluorides

The Mössbauer effect on the 158 keV 5/2^??1/2^? transition in¹⁹⁹Hg, of the order of 10 ppm, has been studied using the current integration technique. The isomer shift between the Hg(I)- and Hg(II)-fluorides as well as the quadrupole splitting in Hg₂Pt and Hg₂F₂ are interpreted in terms of relativistic Hartree-Fock-Slater and Molecular Orbital calculations. The following nuclear parameters could be derived: δ2<=(3.2± l.l)10^?3fm² andQ(5/2^?)=(-0.8±0.4)b. Evidence for an oblate triaxially deformed¹⁹⁹Hg nucleus is derived from particle plus rotor calculations.     

Production ofH(2s) andH(2p) by electron detachment fromH − in collisions with nitrogen and oxygen

¹⁹⁹Hg Fourier Transform NMR studies of various solutions of diverse mercury salts in H₂O and D₂O or in the appropriate protonated and deuterated acids are reported for both Hg ₂ ⁺⁺ and Hg⁺⁺. In the different solutions investigated the¹⁹⁹Hg line positions depend on the concentration of the solution, on the solvents and their isotopic composition and on the temperature of the sample. A ratio of the Larmor frequency of¹⁹⁹Hg and of²H in a Hg(NO₃)₂ solution in dilute DNO₃ is given. Using this ratio and the measured chemical shifts, a ratio of the Larmor frequencies of¹⁹⁹Hg for infinite dilution relative to²H in pure D₂O is given. From this a g_I-factor for¹⁹⁹Hg is derived and compared with the g_I-factor of an optical pumping experiment. The resulting shielding constant is σ^* (hydrated¹⁹⁹Hg⁺⁺ versus¹⁹⁹Hg atom)=?24.32(5) · 10^?4. This yields an atomic reference scale for all measured NMR line shifts of mercury.     

Carbon-13 EPR Hyperfine Interaction in the Complex [Rh(CN)6]in a KCl Host Lattice

The hyperfine interaction with¹³C in nonenriched [Rh(CN)₆]⁴⁻, in a KCl host lattice at 7 K, is measured by continuous-wave X- and Q-band electron paramagnetic resonance, allowing, for the first time, a comparative study of spin densities on the carbon of the axial cyanide in this complex and in the similar [Co(CN)₆]⁴⁻complex. From the experimental data corrected for dipolar interactions,A_iso= 79.80 × 10⁻⁴cm⁻¹andA_anis= 0.76 × 10⁻⁴cm⁻¹.     

W-band31P-ENDOR on the high-affinity Mn2+ binding site in the minimal and tertiary stabilized hammerhead ribozymes

The catalytic activity of the tertiary stabilized hammerhead ribozyme (tsHHRz) is by three orders of magnitude higher than the one of the long-known minimal construct (mHHRz). This gives rise to the question whether the single high-affinity manganese(II) binding site present in both ribozymes is located closer to the cleavage site and the transition state in the tsHHRz than in the mHHRz, which would make a direct involvement of this metal(II) ion in the bond-breaking step more likely. Here, we used W-band³¹P-Davies-ENDOR (electron-nuclear double resonance) to complement earlier reported¹⁴N-ESEEM/HYSCORE (electron spin echo envelope modulation/hyperfine sublevel correlation) studies. The³¹P-ENDOR spectrum of the mHHRz revealed a doublet with a splitting of 8.4(±0.5) MHz but unresolved hyperfine anisotropy. Such a large splitting indicates an inner-sphere coordination of a phosphate backbone group with a significant amount of spin density on the phosphorous nucleus. This is in good agreement with the³¹P isotropic hyperfine constant,A _iso(³¹P), of +7.8 MHz obtained by density functional theory calculations on the structure of the Mn²⁺ binding site as found in crystals of the same ribozyme. This supports the idea that the structure and location of the binding site in the mHHRz is in frozen buffer similar to that found in the crystal. Since the W-band ENDOR spectrum of the tsHHRz also shows a³¹P splitting of 8.4(±0.5) MHz, the local structures of both binding sites appear to be similar, which agrees with the coincidence of the¹⁴N data. An involvement of the high-affinity Mn²⁺ ion in the catalytic step seems therefore unlikely.     

Alpha decay properties of199Rn and199mRn

Theα-decays of¹⁹⁹Rn (E _α = (6.989±0.010) MeV,T _1/2>300ms) and of^199m Rn (E _α = (7.060±0.015) MeVT _1/2=(61 _?2 ⁺³² ) ms) were identified by anα-α-correlation method. They proceed via separated decay paths to¹⁹⁵Po and^195m Po, respectively. The spins of the involved states are discussed by aid of the shell model, and a tentative spin assignment is given.     

L II-electron-gamma correlation in199Hg

The(50L _II?158γ) directional correlation has been measured in¹⁹⁹Hg. The result isA ₂₂=+0.038±0.024, which gives the mixing ratio for the 50keV transition,δ=+0.017±0.006. The accuracy of the method is discussed.     

Transient and pulsed EPR study of17O-substituted methyl-naphthoquinone as radical anion in the A1 binding site of photosystem I and in frozen solution

Quinones have been studied in considerable detail as functional cofactors in membrane-bound protein-cofactor systems, in particular in reaction centers (RCs) of photosynthesis. For both types of RCs, they act primarily as one-electron gates during light-induced charge separation but at very different redox potential. Hydrogen bonding between the RC protein and the two, 1,4-quinone carbonyl groups constitutes a major protein-cofactor interaction in control of function. In contrast to symmetric H-bonding for quinones in isotropic solution, asymmetric H-bonding is a characteristic feature of the quinone binding sites in RC proteins. A simple valence bond model correlates the asymmetry of respective H-bond strength with the asymmetric spin density distribution derived from observable hyperfine couplings of the quinone anion state. Among all quinone-protein systems studied so far, the A₁ acceptor site in photosystem (PS) I exhibits the highest asymmetry. Since the carbonyl groups carry most of the total unpaired electron spin density, isotopic labelling of the carbon (¹³C) and oxygen (¹⁷O) appears to be the proper way to characterize the H-bond asymmetry by hyperfine couplings. Indeed, recent¹³C hyperfine studies, together with data for protons in specific ring substituents, confirm the high asymmetry correlated with only one dominant H-bond in the A₁ site of PS I, which is consistent with the structure model derived from X-ray structure (1JB0) for the ground state of the PS I protein complex.¹⁷O hyperfine tensors measured for the A₁ site of PS I yield high hyperfine coupling constants but very small asymmetry for the two carbonyl groups. The asymmetry is even three times smaller than the already small one observed for the Q_A site of purple bacterial RCs. A small asymmetry is however consistent with previous studies on model systems which showed an insensitivity of the¹⁷O hyperfine coupling to H-bond-induced changes of the unpaired electron spin density. The large¹⁷O hyperfine coupling itself appears to depend on the electrostatics seen by the radical anion. It is slightly larger when A ₁ ^? is part of the functional transient radical ion pair state as compared with the photoaccumulated stable radical anion. Possible explanations and consequences of these results are discussed.     

Lattice dynamical behaviour of Fe(II) spin crossover compounds from57Fe Mössbauer spectroscopy

Temperature-dependent transmission Mössbauer spectroscopy was used to determine the Debye-Waller factors and hyperfine interaction parameters of the Fe(II) spin crossover complexes: Fe(phen)₂(NCS)₂, Fe(bipy)₂(NCS)₂ and Fe(py)₂phen(NCS)₂, and also the non-crossover system Fe(py)₄(NCS)₂. In the spin conversion systems, thef _LS is higher than thef _HS, which indicates different lattice dynamical properties at the metal sites in the¹A₁ and⁵T₂ configurations, and is discussed in relation to the metal-ligand bonding interactions in the two spin states.     

The magnetic hyperfine field at Hg impurities in ferromagnetic Gd

The magnetic hyperfine field at dilute Hg impurities in Gd has been investigated by the conversion electron (e ^–)--time differential perturbed angular correlation (TDPAC) technique. The radioactivities^197m Hg and¹⁹⁹Tl were implanted into Gd foils by means of an isotope separator. TDPAC measurements were performed with the 165 keV-L-conversion electron—134 keV--cascade of¹⁹⁷Hg at different temperatures and with the 334 keV--158 keV-K-conversion electron cascade of¹⁹⁹Hg at 200 K.The regular site occupation probabilities were found to be 15(3)% for an annealed^197m HgGd sample and 29(5)% in unannealed¹⁹⁹TlGd samples.From the magnetic hyperfine interaction frequencies measured for the regular sites at 200 K the magnetic hyperfine fields |H _hf(¹⁹⁷HgGd; 200 K)|=256(13) kG and |H _hf(¹⁹⁹HgGd; 200 K)|=267(7) kG were deduced.On leave from the University of Lisboa, Portugal     

Optically detected E.P.R. and low-field ENDOR of triplet benzophenone

The ENDOR spectrum of ¹³C substituted (carbonyl carbon) triplet excited benzophenone was studied at ca. 100 G applied magnetic field by means of optical detection. The benzophenone was substitutionally dissolved in dibromodiphenylether (DDE). The ENDOR transitions and the E.P.R. transitions were studied as a function of applied field direction in the ab and bc crystal planes. The angle ? between the line joining the phenyl group centres and a principal axis of the fine structure tensor was found to be 23·6° ± 0·02° (standard deviation limited to one set of measurements). The principal axes of the ¹³C hyperfine tensor were within experimental error (±10°) coincident with the fine structure axes. The principal values of the hyperfine tensor were found to be : |A_xx /h| = 43·16 ± 1·84, |A_yy /th| = 22·66 ± 2·50, |A_zz /h| = 10·25 ± 1·30 MHz. The low-field ENDOR does not provide an indication of the signs of these tensor elements, so the value of the isotropic coupling constant cannot be measured. Two values of the anisotropic (dipole) hyperfine tensor elements were deduced on the assumption that the transitions frequencies are mainly determined by interactions between the nuclear spin and electron density on the carbonyl carbon atom. These values were (i) A _xx / ^d /h = 17·82, A_yy /h = -22·68, A_zz /h = -15·14 MHz and (ii) A_xx /h = 39·73, A_yy /h = -26·09, A_zz /h = -13·63 MHz. Set (ii) is consistent with recent calculations of the spin density distribution in triplet benzophenone in which the orbital spin densities are 0·64 for the carbonyl carbon π-orbital, 0·17 for the oxygen π-orbital, and 0·88 for the non-bonding orbital on oxygen (all expressed as fractions of one electron).

Isotope effects on the fine structure constants of triplet benzophenone were measured and found to be consistent with the changes occurring in the spin-orbit coupling with the ground state.

The kinetic parameters for the excitation and de-excitation of the triplet substates were deduced from transient ODMR studies of benzophenone in DDE. The T_z spin state is mainly populated (85–88 per cent) and this is also the most strongly radiative state (k_z ^r = 0·88). The steady-state populations of the three triplet levels are similar.     

Hg-coordination studies of oligopeptides containing cysteine,histidine and tyrosine by 199mHg-TDPAC

In order to study the interaction of histidine- and tyrosine-containing peptide chains with Hg(II), the nuclear quadrupole interaction (NQI) of ^199mHg in the Hg complexes of the oligopeptides Alanyl–Alanyl–Histidyl–Alanyl–Alanine-amid (AAHAA–NH₂) and Alanyl–Alanyl–Tyrosyl–Alanyl–Alanine-amid (AAYAA–NH₂) was determined by time differential perturbed angular correlation and is compared with previous data on Alanyl–Alanyl–Cysteyl–Alanyl–Alanyl (AACAA–OH). The ^199mHg–NQIs depend on the oligopeptide to Hg(II) stoichiometry and indicate that two-fold and four-fold coordinations occur for the bound Hg(II). This revised version was published online in August 2006 with corrections to the Cover Date.