Manifestation of Extracoordination in the Resonance Raman Spectra of Water‐Soluble Cation Co‐Porphyrins

Resonance Raman spectra (RRS) of Co(II) and Co(III)5,10,15,20tetrakis(4Nmethylpyridinium)porphyrin ((Co^II(TmpyP4), and Co^III(TMPyP4)) in aqueous solutions at different pH as well as in organic solvents (methanol, ethanol, DMSO, DMF) are obtained. The increased sensitivity of the oscillation frequencies ₂, ₄, ₈, and ₆ — the markers of the oxidation state of a metal — to the nature of an axial ligand has been revealed. For Co^III(TmpyP4), the shifts of the indicated frequencies in extracoordination have turned out to be twofold larger than those for Co^II(TmpyP4). The spectral effects observed are related to different electron influence of the extraligands on the system of the porphyrin ring. In the case of Co(III)porphyrin, interaction of the d orbitals of the metal and the e _g ^*orbitals of the macrocycle is more efficient since its ionic radius is smaller than for the Co(II)complex. For Co^III(TmpyP4), a linear correlation between the oscillation frequencies ₂, ₄, ₈, and ₆ and the experimental Gutmann parameters characterizing the electronacceptor properties of solvents is found.     

Detection on NMR via the anisotropy of X-rays (X-NMR-ON)

Nuclear magnetic resonance on oriented nuclei has been detected for the first time via the destruction of the anisotropy of characteristic L_x-rays. The new method can be applied to isomeric states which decay only via highly converted transitions, for which the standard NMR-ON technique — detection of NMR via the anisotropy of -rays — is not applicable. The X-NMR-ON technique has been used to measure the magnetic hyperfine splitting of^193mpt (I=1322⁺; E=149.8 keV; T_1/2= 4.3 d) to be ¦ g _NB_HF/h¦=111.3 (3) MHz. with the known hyperfine field of –1280(27) kG the magnetic moment of^193mpt is deduced to be ¦¦=0.7417(14) _N. This magnetic moment differs strongly from the known magnetic moments of the 13/2⁺ isomeric states in Hg and Pb and^195mPt.     

G v,CKM unitarity,neutron decay; WR?

Superallowed Fermi beta-decay is analyzed in the light of new experimental data, new methodology and new treatment of the radiative and charge-dependent corrections. The following values are recommended:G _v /(c) ³=(1.13769±0.00091)×10^–5 GeV^–2;G _v ^* /(c) ³ =(1.15128±0.00084) × 10^–5GeV^–2 whereG _v is purged of radiative corrections suitably for combining withG to gain: ¦V _ud ¦=0.97539±0.00080 which leads to:¦V _ud ¦ ² +¦V _us ¦ ² +¦V _ub ¦²=1.0000+0.0017 and whereG _V ^* is the operational constant, incorporating the inner radiative correction, suitable for use in ordinary nuclear physics. It is noted that present results on the beta-decay of the neutron, when confronted by the above values, are inconclusive as to possible conflict with the minimal standard model and that judgement as to, for example, the intervention of a right-handed sector, should be suspended. The valueG _A ^* =1.2657±0.0030 is also recommended.     

Some more universal scaling laws for critical mappings

We study such nonlinear mappingsx _n +1=F(x _n ;b _cr) of an intervalI into itself for which the Feigenbaum scaling laws hold (i.e., for which b_cr is an accumulation point of bifurcation points). Letx ₀ be a random variable with some absolutely continuous distribution inI. We show in particular that (i) the geometric average distance ofx _n from the nearest point of the attractor decreases liken ^–1.93387; (ii) the geometric average of ¦x _n /x ₀¦ increases liken ^0.60; (iii) the geometric mean distance ¦x _n –y _n ¦ between the iterates of two close-by pointsx ₀,y ₀ asymptotically tends towards a value ¦x ₀–y ₀¦^0.77. These-and other-properties are also borne out from a simple probabilistic model which depicts the evolution as a random walklike process.     

Parity violation in the 17/2−–17/2+ doublet in93Tc

The parity-violating mixing of the 17/2^– and 17/2⁺ levels in⁹³Tc nuclei, polarized by the tilted multifoil interaction, was measured by the observation of the forward-backward-ray asymmetry. The nuclear polarization, induced by the tilted multifoils, was measured directly for the neighboring^88,90Zr isomers. The forward to backward asymmetry was determined to be A=(2.5±2.1) 10^–3 which implies a parity violating matrix element ¦H _PV )¦=(4.0±3.7)meV.     

Critical behavior of the two-dimensional first passage time

We study the two-dimensional first passage problem in which bonds have zero and unit passage times with probabilityp and 1–p, respectively. We prove that as the zero-time bonds approach the percolation thresholdp _c, the first passage time exhibits the same critical behavior as the correlation function of the underlying percolation problem. In particular, if the correlation length obeys(p) ¦p–p _c¦^–v, then the first passage time constant satisfies(p)¦p–p _c¦^v. At p_c, where it has been asserted that the first passage time from 0 tox scales as ¦x¦ to a power with 0<<1, we show that the passage times grow like log ¦x¦, i.e., the fluid spreads exponentially rapidly.     

Intense spontaneous amplified emission of Li2 diffuse violet bands in the 4400 Å region

We report observation of intense spontaneous amplified radiation of Li₂ diffuse violet band in the 4100–4900 Å region. The radiation is strongly enhanced when the lithium vapor in a heat pipe is optically pumped with a pulsed dye laser with the output wavelength tuned to near the Li 2s–4s two-photon resonance transition. The diffuse violet band can probably be assigned to a recently reported triplet bound-free (2³ _g a ³ _u ⁺ ) transition. It is found that the productions of the molecular diffuse band are contributed from Li atoms as well as Li₂ molecules. The excitation functions and their dependence on laser power density are presented and the mechanisms for producing the diffuse bands are discussed.Department of Physics, National Central University, Chung-Li, Taiwan, Republic of Chinabl]References     

Magnetic properties of the cyclic spincluster Fe6:bicine

The magnetic properties of the cyclic compound [Fe₆(bicine)₆] LiClO₄ ^. 2MeOH are reported. The cluster Fe₆(bicine)₆ forms an antiferromagnetically coupled ring structure of Fe ^III ions. The magnetic susceptibility is measured between 2 and 300 K and yields the exchange coupling of J/k _B = - 27.5±0.5 K. The field dependence of the magnetic moment is studied at 3 and 6 K in magnetic fields up to 5 T. The zero-field splitting of the first excited spin states with S = 2 and 3 are determined by ESR at 94 GHz. The intra-molecular interactions of the Fe ^III ions are analyzed and the on-site anisotropy of the Fe ^III due to the ligand-configuration is determined to d /k _B = - 0.633±0.008K. Received 28 October 2002 / Received in final form 22 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: bernd@piobelix.physik.uni-karlsruhe.de     

μ+SR in magnetically ordered BCC metals: Local fields, μ+ sites,quantum diffusion,and strain effects

The paper gives a critical discussion of the procedures for extracting from the ⁺SR signals obtainable on magnetically ordered metals information on ⁺ sites, on local lattice distortions induced by the ⁺, on the local magnetic fields felt by the ⁺, and on quantum diffusion. Results for-Fe are: ⁺ occupy O sites, the tetragonality of the elastic double-force tensor isA–B 2eV, the dipolar magnetic field acting on the ⁺ isB _dip=(0.66±0.02)T. Using this information ⁺ hopping rates and diffusivities in Fe are deduced and compared with diffusivities obtained for hydrogen and deuterium. From this it is concluded that hydrogen in Fe diffuses via the adiabatic mechanism. In addition, the paper contains a brief summary of the theoretical background required for taking advantage of the rather large ¦A– B¦ values expected for ⁺ at O sites in bcc metals in order to gain information on the effects of energy asymmetries between neighbouring ⁺ sites on the ⁺ hopping rates.     

Search for possible anapole and electric dipole moments of the proton on the basis of the pp ⇌ e+ e− annihilation reaction

Differential and total cross sections are found for the formation of an electron-positron pair during the annihilation of longitudinally polarized protons and antiprotons (pp e⁺ e^–) and for the inverse reaction (e⁺ e^- pp) in the single-photon approximation, account is taken of the anapole and electric dipole moments of the proton, which violate C, P, and T parity. Possible ways to determine the square moduli of the form factors for the anapole [G₁(q²)] and electric dipole [G₂(q²)] moments and to determine the relative phase of the form factors F_e(q²) and G₂(q²) [F_m(q²) and G₁(q²)] are pointed out. Estimates are found for ¦(G₁q²)¦² and ¦G₂(q²) ¦² with q² = –6.8 (GeV/c)².Translated from Izvestiya VUZ. Fizika, No. 8, pp. 59–65, August, 1970.The authors thank Professor A. A. Sokolov, Professor I. M. Ternov, and Yu. M. Loskutov for discussions of these results.     

Precise measurement of the quadrupole moment of β-emitting12B

Hyperfine interactions of¹²B(I ,T _1/2=21 ms) implanted in the substitutional site of B atoms (stable) in a (single crystal like) BN (hexagonal) was studied by use of a -NMR detection. For efficient and simple measurements, the conventional -NMR has been modified as a new nuclear quadrupole resonance technique (NNQR). For the present case with the nuclear spinI=1 the detection efficiency is improved about 30 times compared with the one with the old method. The quadrupole moment of¹²B was determined precisely as ¦Q(¹²B; 1⁺)¦=13.21±0.26 mb.     

The tortuosity of occupied crossings of a box in critical percolation

We consider the length of an occupied crossing of a box of size [0,n]×[0, 3n] ^D–1 (in the short direction) in standard (Bernoulli) bond percolation on ^D at criticality. Let ¦s _n¦ be the length of the shortest such crossing. It is believed that ¦s _n¦ ^1+c in some sense for somec>0. Here we show that if the correlation length(p) satisfies (p)p _c}–p) ^– for some <1, then with a probability tending to 1, ¦s _n¦>/C ₁ n ^1/(logn)^–(1–)/. The assumption (p)C ₃(p _c–p)^– with <1 has been rigorously established^(1,2) for largeD, but cannot hold⁽³⁾ forD=2. In the latter case, let ¦l _n¦ be the length of the lowest occupied crossing of the square [0,n]². We outline a proof ofP _pc(¦l_n¦ n ^1+c)n ^– for somec, >0. We also obtain a result about the length of optimal paths in first-passage percolation.     

Nuclear magnetic moment of 12 d 11/2− 131mXe

NMR-ON measurements were performed on^131mXe (I=11/2^–; T_1/2=12.0 d) in Fe, the sample being prepared by recoil implantation after the¹³⁰Te(,3n)^131mXe compound reaction at E=40 Mev. The hyperfine splitting _NB_HF/h¦, extrapolated to zero external magnetic field, was found to be 209.9(1) MHz. Taking B_HF=+1523(8) kG for the hyperfine field of XeFe, the magnetic moment of^131mXe is deduced to be (–)0.994(5) _N. As a byproduct, the zero-field hyperfine splitting of^129mXe (I=11/2^–; T_1/2=8.9d) in Fe was measured as 188.1(1) MHz, with which a magnetic moment of (–)0.891(5) _N is deduced for^129mXe.     

Dipolar magnetic field and fermi contact field at the μ+ site in α-Fe at very low temperatures

In a longitudinal ⁺SR experiment on a high-purity-Fe single crystal sphere magnetically saturated in a 111 direction damped oscillations (wiggles) were observed in a temperature range 30 mK to 600 mK and in a certain regime of applied magnetic fieldsB _appl. Meassurements of the wiggle frequency as a function ofB _appl give us directly the Fermi fieldB _Fermi=(–1.13±0.02)T and the dipolar magnetic field ¦B _dip ¦=(0.66±0.03)T.B _dip was used to determine the prefactor in the Arrhenius law obeyed by the ⁺ hopping rate between 100 K and 1000 K. A comparision with the corresponding values for protons and deuterons suggests diffusion via the adiabatic mechanism.     

Paramagnetic Proton Nuclear Spin Relaxation Theory of Low-Symmetry Complexes for Electron Spin Quantum NumberS=

A generalization of the modified Solomon–Bloembergen–Morgan (MSBM) equations has been derived in order to describe paramagnetic relaxation enhancement (PRE) of paramagnetic complexes characterized by both a transient (Δ^ZFS_t) and a static (Δ^ZFS_s) zero-field splitting (ZFS) interaction. The new theory includes the effects of static ZFS, hyperfine coupling, and angular dependence and is presented for the case of electron spin quantum numberS= , for example, Mn(II) and Fe(III) complexes. The model gives the difference from MSBM theory in terms of a correction term δ which is given in closed analytical form. The theory may be important in analyzing the PRE of proton spin–lattice relaxation dispersion measurements (NMRD profiles) of low-symmetry aqua–metal complexes which are likely to be formed upon transition metal ions associated with charged molecular surfaces of biomacromolecules. The theory has been implemented with a computer program which calculates solvent water protonT₁NMRD profiles using both MSBM and the new theory.     

Estimates of general Mayer graphs. IV. On the computation of Gaussian integrals by the star-mesh transformation

We point out that, to compute by hand a Gaussian integral exp · (– _LL y _l r _ij ² d r _n+1 ...d r _n+k , where the sum runs over all linesL = (i,j) of a graph andr _ij = ¦r _i –r _j ¦, the simplest way is to use the star-mesh transformation, well known in electrical network theory. We apply this to test, on a relatively complicatedn-graph, the accuracy of an estimation method that we proposed elsewhere [Phys. Lett. 62A:295 (1977)].     

Exchange-coupling across SiO

Strongly temperature-dependent ferromagnetic exchange coupling is observed between Fe films separated by an amorphous SiO barrier. Heating reversibly enhances the coupling strength which monotonically decreases with increasing SiO thickness. AtT=40K the coupling disappears for d_SiO20Å whereas at room temperature it persists up to a barrier thickness of 60 Å. The coupling strengthJ is determined by externally compensating the exchange field of samples grown on an antiferromagnetically biased Fe/Cr/Fe structure. It amounts toJ2·10^–6 J/m² for a sample with d_SiO=25 Å atT=300K. As a tentative explanation we propose that impurity or defect states within the large mobility gap of SiO carry the magnetic interaction across the insulating barrier.     

Bohm trajectory and Feynman path approaches to the “Tunneling time problem”

A comparison is made between the Bohm trajectory and Feynman path approaches to the long-standing problem of determining the average lime taken for a particle described by the Schrödinger wave function to tunnel through a potential barrier. The former approach follows simply and uniquely from the basic postulates of Bohm's causal interpretation of quantum mechanics; the latter is intimately related to the most frequently cited approaches based on conventional interpretations. Emphasis is given to the fact that fundamentally different transmission (T)-reflection (R) decompositions, particlelike and wavelike respectively, are central to the two methods: ¦¦²=[¦¦²]_T+[¦¦²]_R (Bohm trajectory approach); =_T+_R (Feynman path approach).     

Gap exponents for percolation processes with triangle condition

A study is made of the gap exponents for percolation processes with the triangle condition in the subcritical region. It is show that the gaps are given by _t =2 fort=2, 3,. Scaling theory predicts thatP _p (¦C ₀¦S(p))–(p _c –p) andE _p (1/¦C ₀¦; ¦C ₀¦S(p))–(p _c –p)³, whereS(p) is the typical cluster size. It is found that (p _c –p)P _p (|C ₀S(p) ^1–)(p _c –p)^1–2 and (p _c –p)³E _p (1/|C ₀|;|C ₀|S(p) ^1–))(p _c –p)^3–4.     

NMR-ON on196,197m,198,198m,200mAu in Fe and Ni

The zero-field hyperfine splitting frequencies of a series of Au isotopes in Fe and Ni have been determined with nuclear magnetic resonance on oriented nuclei. The results are:. For¹⁹⁸Au(2^–) in Fe the quadrupole splitting could be resolved. The results are ¦g_NB_HF/h|=259.48 (3) MHz and e²qp/h=–2.08(4) MHz. Our measurements show that most hyperfine splittings published on these isotopes have been incorrect. The quadrupole splitting of¹⁹⁸AuFe disagrees in magnitudeand sign from the value reported by single-passage NMR on oriented nuclei. The following nuclear quantities are deduced: (^197mAu,11/2^–)=5.98(9) _N; (^198mAu, 12^–)=5.85(9) _N; (^200mAu, 12^–)=5.90(9) _N; Q(¹⁹⁸Au,2^–)/Q(¹⁹⁹Au, 3/2⁺)=1.37(3). Our measurements show further that the non-contact hyperfine field for Au in Ni is smaller than assumed previously, and that the magnetic hyperfine splitting frequency of¹⁹⁷AuFe known from NMR is inconsistent with the magnetic hyperfine splitting frequencies of^{198, 199}AuFe.