Hyperfine structure in hydrogen and helium ion

QED theory of the hyperfine splitting of the 1s and 2s state in hydrogen isotopes and helium-3 ion is considered. We develop an accurate theory of a specific difference 8E_HFS(2s)−E_HFS(1s). We take into account higher-order QED and nuclear structure effects. In particular, we found the vacuum polarization contribution in order α(Zα)³E_F and examined the recoil contribution in order (Zα)³m/M and thus completed a calculation of the fourth order QED corrections. The higher-order nuclear structure contributions were also analysed. The theoretical predictions reported here are now of a higher accuracy than the experiment. The study of the difference provides the most accurate test (at a level of a part in 10⁸) of the QED theory of ns HFS up to date. The theory agrees with most of the experimental data.     

2s Hyperfine splitting in light hydrogen-like atoms: Theory and experiment

Since the combination D ₂₁ = 8f _HFS(2s)-f _HFS(1s) of hyperfine intervals in hydrogen and light two-body hydrogen-like atomic systems weakly depends on the nuclear structure, comparison between theory and experiment can be sensitive to high order QED corrections. New theoretical and experimental results are presented. Calculations have been performed for the hydrogen and deuterium atoms and for the helium-3 ion. Experiments on the 2s hyperfine splitting (responsible for the dominant contribution to the error in D ₂₁) have been conducted for hydrogen and deuterium. The theory and experiment are in good agreement, and their accuracy is comparable to that attained in verifying the QED theory of the hyperfine splitting in leptonic atoms (muonium and positronium).     

Lamb shift in light muonic atoms

The QED contributions to the 2s?2p _3/2 splitting in muonic⁴He are recalculated with the aim of providing a check on previous theoretical calculations, and clarifying a possible small discrepancy in the comparison between theory and experiment (no significant discrepancy is found in the present work). Numerical results for other light nuclei are presented.     

Muon Knight shift in palladium

The Knight shift at positive muons implanted in pure palladium has been measured as a function of temperature from 19.8 to 883 K. The Knight shift variation is strictly proportional to the Pd magnetic susceptibility with ΔK^μ/Δ_x=-(0.43±0.02) mole/emu=-(2.39±0.11)kG/μ_B. A temperature independent term K^μ(x=0)=+45±10 ppm is found. The results are discussed in terms of the electronic structure of H in Pd.     

QCD studies with e+e− annihilation data at 161 GeV

We have studied hadronic events produced at LEP at a centre-of-mass energy of 161 GeV. We present distributions of event shape variables, jet rates, charged particle momentum spectra and multiplicities. We determine the strong coupling strength to be α_s(161 GeV) = 0.101±0.005(stat.)±0.007(syst.), the mean charged particle multiplicity to be 〈n _ch〉(161 GeV) = 24.46 ± 0.45(stat.) ± 0.44(syst.) and the position of the peak in the ξ_p = ln(1/x _p) distribution to be ξ₀(161 GeV) = 4.00 ±0.03(stat.)±0.04(syst.). These results are compared to data taken at lower centre-of-mass energies and to analytic QCD or Monte Carlo predictions. Our measured value of α_s(161 GeV) is consistent with other measurements of α_s. Within the current statistical and systematic uncertainties, the PYTHIA, HERWIG and ARIADNE QCD Monte Carlo models and analytic calculations are in overall agreement with our measurements. The COJETS QCD Monte Carlo is in general agreement with the data for momentum weighted distributions like Thrust, but predicts a significantly larger charged particle multiplicity than is observed experimentally.     

Orientational and positional disorder of ions and its freezing in the CsNO2-TlNO2 system2

The heat capacities of Cs_0.695Tl_0.305NO₂ (Specimen I) and Cs_0.385Tl_0.615NO₂ (Specimen II) have been measured between 14 and 350 K. Specimen I underwent a phase transition at (197.7 ± 0.1) K, with ΔS = (19.2 ± 1.5) JK^?mol^?, and specimen II at (214.5 ± 0.2) K, with ΔS = (5.4 ± 1.0) JK^?1mol^?1, respectively. Above the phase transition, an exothermic temperature drift due to phase separation was observed. Annealing of the sample at 203 K for 300 hr brought about complete phase separation. The solid solution system annealed at 203 K gave two heat capacity peaks at (203.3 ± 0.1) K, with ΔS = (13.8 ± 0.8) JK^?1 mol^?1, and (242.4 ± 0.2) K, with ΔS = (10.6 ± 1.3) JK^?1 for Specimen I, and at (203.0 ± 0.1) K with ΔS = (6.7 ± 0.5) JK^?1 mol^?1, and (257.5 ± 0.2) K with ΔS = (17.9 ± 1.7) JK^?1 mol^?1 for Specimen II. The phase diagram of the CsNO₂-TlNO₂ binary system was constructed on the basis of DTA, heat capacity and dielectric measurements. In the metastable phase, the existence of a residual entropy due to the freezing of a random distribution of Cs⁺₁ and Tl⁺ cations in addition to the orientational disorder of the NO₂^?1 ion was confirmed by a comparison of entropies of the stable and the metastable phases.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.     

Far infrared spectrum and spectroscopic constants of AsH3 in the ground state

The far ir spectrum of arsine, AsH₃, was recorded in the range 25–100 cm^?1 with a resolution of approximately 0.004 cm^?1. ΔJ = +1, ΔK = 0 rotational transitions were measured and assigned up to J″ = 12. These transitions, together with the presently available microwave and submillimeter-wave data and ground state combination differences, were analyzed on the basis of a rotational Hamiltonian which includes Δk = ±3 and Δk = ±6 interaction terms. The derived ground state molecular parameters reproduced the transition frequencies of both allowed and “perturbation allowed” transitions within the accuracy of the measurements. The equilibrium structure was determined for the AsH₃ molecule.     

Determination of fine structure intervals in a series of excited sodium D states using doppler free two-photon spectroscopy

Using Doppler free two-photon spectroscopy technique, we have measured the absolute values of fine-structure (fs) intervals in a series of excited sodium n²D states (n = 3,6,7, and 8). We have shown the structures are inverted and our measured values for these states are: Δ_fs(3²D) = -1523 ± 8 MHz, Δ_fs(6²D) = -385 ± 5 MHz, Δ_fs(7²D) = -253 ± MHz, and Δ_fs(8²D) = -173 ± 10 MHz.     

Second indirect band gap in silicon

We report the first observation of the г₂₅→L₁ (second indirect) transition in Si based on optical absorption studies. The energy, (1650 ± 10) meV, measured for this critical point shows that there remains a large discrepancy between theoretical band structure calculations and experimental results for this material.     

Mössbauer spectroscopy and DFT calculations on all protonation states of the 2Fe-2S cluster of the Rieske protein

The Thermus thermophilus Rieske protein (TtRP) contains a 2Fe-2S cluster with one iron (Fe-Cys) coordinated by four sulfur atoms (2xS^2? and 2xCys) and one iron (Fe-His) by two sulfur and two nitrogen atoms (2xS^2?, His134 and His154). Here, the protein is investigated at three pH values (6.0, 8.5 and 10.5) in order to elucidate the protonation states of the His-ligands. Examination of the effect of protonation on the electronic structure of the cluster via Mössbauer spectroscopy gives a deeper understanding of the coupling of electron transfer to the protonation state of the His-ligands. Two components (1 referring to Fe-Cys and 2 to Fe-His) with parameters typical for a diamagnetic [2Fe-2S]²⁺ cluster are detected. The Mössbauer parameters and the protonation state clearly correlate: while δ remains almost pH-independent with δ ₁ (pH6.0) =?0.23 (±?0.01) mms^??1 and δ ₁ (pH10.5) =?0.24 (±?0.01) mms^??1 for Fe-Cys, it decreases for Fe-His from δ ₂ (pH6.0) =?0.34 (±?0.01) mms^??1 to δ ₂ (pH10.5) =?0.28 (±?0.01) mms^??1. ΔE _Q changes from ΔE _Q1 (pH6.0) =?0.57 (±?0.01) mms^??1 to ΔE _Q1 (pH10.5) =?0.45 (±?0.01) mms^??1 and from ΔE _Q2 (pH6.0) =?1.05 (±?0.01) mms^??1 to ΔE _Q2 (pH10.5) =?0.71 (±?0.01) mms^??1. Density functional theory (DFT)-calculations based on the crystal structure (pdb 1NYK) (Hunsicker-Wang et al. Biochemistry 42, 7303, 2003) have been performed for the Rieske-cluster with different His-ligand protonation states, reproducing the experimentally observed trend.     

Determination of the Spin–Spin Coupling Constant in Hydrogen Deuteride HD and Estimates of the Manifestation of Axion-Like Particles

An experimental value of the spin–spin coupling constant in deuterated molecular hydrogen HD has been obtained, J _pd = (43.112 ± 0.005) Hz (300 K), while investigating two gaseous samples at pressures of 95 and 155 atm. The experimental result does not coincide with Jpd = (43.31 ± 0.05) Hz that was calculated theoretically by Helkager et al. The observed discrepancy ΔJ _pd ≈ (0.20 ± 0.05 Hz) may point to a manifestation of the involvement of light pseudo-scalar (axion-like) bosons with a mass m _a ≈ 1 keV/c² in the spin–spin coupling of the HD proton and deuteron.     

M-dependence of collisional transfer of rotational energy in OCS mixtures

Collision-induced transitions between rotational levels of OCS in the ground vibrational state have been investigated by steady-state microwave double resonance, with the M sublevels separated by a Stark field. The (2 ← 1)_P-(1 ← 0)_S, (3 ← 2)_P-(1 ← 0)_S, and (4 ← 3)_P-(1 ← 0)_S systems have been studied for pure OCS and for mixtures with excess CH₃OH, He, and H₂. For four-level systems having dipolar connections (ΔJ = 1; ΔM = 0, ± 1; parity ± ? ?) between pump and signal levels, it is found for OCS and the OCS-CH₃OH mixture that the dipole-type ΔJ = 1 transitions always dominate the collisional transfer, but for the OCS-He and OCS-H₂ mixtures that ΔJ = 2 quadrupole-type transitions are dominant. For all four collision partners, significant ΔJ = 2 and ΔJ = 3 collisional transfer is observed in some systems, indicating the presence of high-order terms in the collisional interaction.     

Spectroscopic study of microwave discharge as a radiation source for transition probability measurements

The optical properties of a discharge in a mixture of helium (200 torr) and hydrogen (0.1 torr) were investigated. Line intensities were measured photoelectrically. Partial LTE is demonstrated by the linearity of plots of log(Iλ/gA) vs E. The temperatures T_He = 3300 and T_H = 3400 K are obtained from the slopes of the plots for He and H, respectively. Relative A-values for the hydrogen Balmer lines derived from the helium temperature agree with theoretical values within ±20 per cent. The uncertainties (≤ 7 per cent) estimated from the discrepancy between the temperatures are smaller than those (±10 per cent) due to errors in the observed line intensities.     

Investigation of (n, 2n) reactions by the evaporation process

The (n, 2n) cross sections for about 80 nuclei ranging fromA=45 to 209 were calculated using the evaporation model. The calculation was performed for incident energiesE _n which satisfy the conditionU _R =E _n +Q _n ,2n=6±1 MeV. For 11 nuclei in the above mass region, (n, 2n) excitation functions were calculated from threshold to 20 MeV. In all calculations a single set of input parameters was consistently used. The influence of the level-density parameter and neutron cross sections on the evaporation model was tested. All calculated results were compared with experimental data. The systematic discrepancy between experimental data and evaporation calculations leads to the necessity of introducing the preequilibrium emission mechanism.     

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.     

Microwave spectrum and selenol internal rotation of 2-propaneselenol

Microwave spectra of 2-propaneselenol and its deuterated species were measured and assigned for the gauche and trans isomers. The double minimum splittings of the gauche isomers were directly observed from b-type transitions, which were assigned with the aid of a double resonance technique. Rotational constants and torsional splitting of the gauche isomer of the parent species were determined to be A = 7802.50 ± 0.75, B = 2847.68 ± 0.04, C = 2242.03 ± 0.03, ΔA = ?2.52 ± 0.74, ΔB = 0.02 ± 0.05, ΔC = ?0.34 ± 0.03, and Δν = 368.91 ± 0.94 MHz, where ΔA, and ΔB, and ΔC are the differences of the rotational constants between the (+) and (?) states. From the torsional splittings and the energy differences of the two isomers of the parent and SeD species, Fourier coefficients of the selenol internal rotation potential function were determined to be V₂ = ?88 ± 15, V₃ = 1543 ± 29 cal/mole on the assumption of V₁ = 0. Dipole moments and their components were also obtained for the two isomers.     

Infrared diode-laser spectrum of the CH3CN ν2 band: Analysis of local resonances with ν6±1 + 2ν8±2, ν4 + ν7±1 + ν8±1, ν4 + ν6±1, ν4 + ν7±1, and 2ν70 + ν8±1 states

Fifty-one sections of infrared diode-laser spectra of acetonitrile have been measured in the region from 2283.5 to 2235.7 cm^?1. About 450 transitions belonging to the ν₂ band have been assigned for K ≦ 7 and J ≦ 44. Anomalies found in the rotational structure have been proven to be due to five local resonances. Observed transition frequencies have been fitted by a least-squares method to a model which includes Fermi-type resonances (Δk = 0, Δ? = ± 3n) with ν₆^±1 + 2ν₈^±2 and ν₄ + ν₇^±1 + ν₈^±1 states, x, y-type Coriolis resonances (Δk = ±1, Δ? = ?3n ± 1) with ν₄ + ν₆^±1 and ν₄ + ν₇^±1 + ν₈^±1 states, and a centrifugal-distortion-type resonance (Δk = ±2, Δ? = ?3n ± 2) with a 2ν₇⁰ + ν₈^±1 state. The 11 × 11 dimensional energy matrix has been diagonalized in order to obtain the perturbed energy levels. The standard deviation for the fit is 1.075 × 10^?3 cm^?1. The molecular constants determined are also listed.     

Adsorption and desorption of CO and H2 on Rh(111): Laser-induced desorption

Isosteric heats of adsorption ΔH_ad of CO and sticking coefficients S for CO and H₂ on Rh(111) are determined by laser-induced thermal desorption (LITD) in which a pulsed laser beam is focused onto the surface, and rapid local heating yields a desorption signal that is proportional to the adsorbate coverage θ. ΔH_ad for CO falls from 32.0±2 kcal/mol at low coverage to 14 kcal/mol at saturation, and the desorption pre-exponential factor v_d decreases from 10^14±0.5 to 10¹⁰ s^-1. ΔH_ad, v_d, and S of CO all decline sharply above θ = 0.2, corresponding to the occupation of a second binding state. Sticking coefficients for CO and hydrogen indicate precursor intermediates in adsorption.