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.     

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.     

Low energy photoelectron spectroscopy of solids. Aspects of experimental methodology concerning metals and insulators

Both He(I) and He(II) ultraviolet photoelectron spectra (UPS) for metals (Ag, Au) and thin solid films of organic (anthracene) and inorganic compounds (LiF, LiCl, LiBr, LiI, NaF, NACl, Li₂SO₄, NaOH) are presented. The results of measurements on two different spectrometers have shown that both the bias voltage, V_b, applied to the solid sample, and the angle of incidence, Ø, of the photon beam with the sample are crucial to the accurate determination of the work function (metals) and binding energies (insulators). The true binding energy of a band in the UPS with respect to the vacuum level, E_b^vac, is defined as the minimum value of (hv - ΔE), where ΔE is the energy difference between the threshold of the SEED, E_T, and the band maximum. ΔE is maximized at low values of ø and of V_b. The intensity of photoelectron emission (signal) increases with both ø (2–30°) and V_b (5–20 V). It is recommended that the variation of ΔE with both ø and V_b should be observed in any determination of E_B^vac.     

Current induced deformation of charge density waves in orthorhombic TaS3

The low electric field ohmic resistance R of orthorhombic TaS₃ measured at 90 and 120 K well below the Peierls transition temperature depends on the product of a temperature difference ΔT applied along the sample and the sign of a previously applied current pulse if this pulse is larger than threshold for non-ohmic conductivity. This resistance change is about ΔR/RΔT ∽ 1×10^-3 K^-1 for a pure sample and ΔR/RΔT ∽ 6×10^-3 K^-1 for a slightly electron irradiated one at 90 K. The relative resistance change is insensitive to the sample length. We deduce that the CDW current changes inhomogeneously the Peierls gap E_g. ΔE_g < O at the contact where the CDW current enters and ΔE_g > O at the exit. The effect is attributed to a CDW current induced inhomogeneous deformation of the CDW itself.     

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.     

Universal estimate of the gap for the Kac operator in the convex case

The aim of this paper is to prove that ifV is a strictly convex potential with quadratic behavior at ∞, then the quotient μ₂/μ₁ between the largest eigenvalue and the second eigenvalue of the Kac operator defined on L²(? ^m ) by exp ?V(x)/2 · exp Δ_x · exp ?V(x)/2 where Δ_x is the Laplacian on ? ^m satisfies the condition: $${{\mu _2 } \mathord{\left/ {\vphantom {{\mu _2 } {\mu _1 {{ \leqslant \exp - \cosh ^{ - 1} (\sigma + 1)} \mathord{\left/ {\vphantom {{ \leqslant \exp - \cosh ^{ - 1} (\sigma + 1)} {2,}}} \right. \kern-\nulldelimiterspace} {2,}}}}} \right. \kern-\nulldelimiterspace} {\mu _1 {{ \leqslant \exp - \cosh ^{ - 1} (\sigma + 1)} \mathord{\left/ {\vphantom {{ \leqslant \exp - \cosh ^{ - 1} (\sigma + 1)} {2,}}} \right. \kern-\nulldelimiterspace} {2,}}}}$$ where σ is such that HessV(x)≥σ>0.     

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.     

Diode laser spectra of the ν2 band of H212CO and H213CO

The Q-branches of the ν₂ (CO stretch) band of H₂¹²CO and H₂¹³CO have been studied in high resolution using an infrared diode laser. Accurate upper state constants, including A, B, C, Δ_J, Δ_JK, Δ_K, and H_K, were determined from an analysis of the data for 97 lines of H₂¹²CO and 79 lines and H₂¹³CO and compared with previous reported values. Band centers were also determined and reported as 1746.009 ± 0.002 cm^?1 for H₂¹²CO and 1707.981 ± 0.002 cm^?1 for H₂¹³CO.     

Overview on neutrinos and the Daya Bay experiment

Neutrinos are elementary particles in the Standard Model. Neutrino oscillation is a quantum mechanical phenomenon beyond the Standard Model. Neutrino oscillation can be described by two independent mass-squared differences Δm ₂₁ ² , Δm ₃₁ ² (or Δm ₃₂ ² ) and a 3 × 3 unitary matrix, containing three mixing angles θ ₁₂, θ ₂₃, θ ₁₃, and one charge-parity (CP) phase. θ ₁₂ is about 34° and determined by solar neutrino experiments and the reactor neutrino experiment KamLAND. θ ₂₃ is about 45° and determined by atmospheric neutrino experiments and accelerator neutrino experiments. θ ₁₃ can be measured by either accelerator or reactor neutrino experiments. On Mar. 8, 2012, the Daya Bay Reactor Neutrino Experiment reported the first observation of non-zero θ ₁₃ with 5.2 standard deviations. In June, with 2.5× previous data, Daya Bay improved the measurement of sin²2θ ₁₃ = 0.089 ± 0.010(stat) ± 0.005(syst).     

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.     

Investigation of the decay rate for71Ge in chemical compounds and calibration of the Mössbauer isomer shift of the 67 keV γ-transition of73Ge

Changes of the radioactive decay rate of⁷¹Ge (T _1/2=11.43 days) have been studied experimentally for⁷¹Ge in some compounds of bivalent and quadrivalent germanium. Relative changes Δλ/λ of the electron capture probability have been measured, and the chemical changes Δρ(0) of the electron density at the germanium nuclei have been determined from these measurements. Values for the Mössbauer isomer shift calibration constants for the 67 keV γ-transition of⁷³Ge have been estimated:C=δ/Δρ(0)=(0.061±0.020) mm·s^?1/a.u., Δ〈r ²〉=(21±7)·10^?3 fm², ΔR/R=(6.9±2.3)·10^?4.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

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.     

First direct observation of strong interaction spin-orbit effects in antiprotonic atoms

The strong ¯p-nucleus spin-orbit interaction was investigated in a measurement of the strong-interaction effects of the 9→8 transition in ¯p ¹⁷⁴Yb at the Low-Energy Antiproton Ring (LEAR) at CERN. This measurement was part of an experimental programme where, for the first time, the fine-structure components of the last observable X-ray transition in a ¯p atom, which carries information on the strong ¯p-nucleus interaction, were resolved and studied individually. The observed splitting ΔE _exp=2408±26 eV consists of the electromagnetic fine-structure splitting ΔE _FS=2350 eV and an additional splitting Δ?=58±26 eV. In addition, one finds a significant difference in the level widths of Δ=195±59 eV with the larger value_?=1216±41 eV for the lower fine-structure level. This experiment follows an earlier measurement on ¯p ¹³⁸Ba, where the transition 8→7 is influenced by the strong interaction. In this case, however, the fine-structure components could not be resolved. The results for¹⁷⁴Yb may be attributed to a spin-orbit (LS) term in the complex strong-interaction potential.     

Quantum beats in two-photon resonance fluorescence

The two-photon resonance fluorescence spectrum of a three-level atom is shown to consist of the low frequency modes in addition to the high frequency ones in the limit of high photon densities. The spectral function for the low frequency modes consists of two lorentzian lines describing: the peak occuring at the renormalized beat frequency Δ₊ and that of the zero-photon excitation at the frequency Δ_-, where Δ_±=Δ-3Ω²/2ω_a±Ω²u/2ω_a, u²=1+(2Δω_a/Ω ²)². Here, 2Δ is the energy splitting between the two excited states, ω_a is the photon energy of the pump field and Ω is the Rabi frequency. The peak at the renormalized beat frequency Δ₊ occurs provided that the condition (2Δω_a/Ω²)² > 1 is satisfied. The two-photon laser spectroscopy is expected to be a useful tool for the observation of the low frequency modes in question.     

Identification of hyperfine structure components of the iodine molecule at 640 nm wavelength

The frequencies and the relative intensities of rotation-vibration transitions of ¹²⁷I₂, ¹²⁹I₂ and ¹²⁷I¹²⁹I near the HeNe laser emission wavelength of 640 nm have been calculated. Interpolation formulas for the differences of the electric quadrupole constants ΔeQq and of the spin-rotation constants ΔC of ¹²⁷I₂ are given. Most of the weak saturated-aborption lines, elsewhere published, have been identified as cross-over and forbidden lines of the transitions P(10)8-5 and R(16)8-5.     

Inversion-rotation spectrum and spectroscopic parameters of 14ND3 in the ground state

The far-infrared spectrum of ¹⁴ND₃ has been recorded in the region between 30 and 220 cm^?1 at a resolution, before deconvolution, of approximately 0.004 cm^?1. ΔJ = +1, ΔK = 0, a ← s and s ← a inversion-rotation transitions have been measured and assigned up to J″ = 19. These transitions, the pure inversion-microwave transitions and ground-state combination differences from the analysis of the ν₂ and ν₄ bands have been fitted simultaneously to an inversion-rotational Hamiltonian which includes Δk = ±3 and Δk = ±6 interaction terms. The ground-state spectroscopic parameters obtained in this way reproduce the transition frequencies within the accuracy of the measurements.     

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.     

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.     

Electronic properties of charged fullerenes characterized by EPR and Vis-NIR spectroscopy

EPR and Vis-NIR absorption spectra have both been measured for clarification of contradictory statements about the para-and diamagnetic states of fullerenes. Thereby identification of one sharp EPR signal in solution at room temperature to C ₆₀ ^? (g=2.000±4.0001; ΔB=0.07±0.01 mT) could be made upon using different fullerene sources (TechnoCarbo, Hoechst) and methods of anion generation (chemically, electrochemically, and photochemically). This fact is also supported by the similar observation for a monosubstituted derivative (g=1.9999; ΔB=0.10 mT), in which a small broadening of this sharp signal is found originating from additional¹H hyperfine interactions. Furthermore theg-values of the radical anions of C₆₀ increase with charge (g(C ₆₀ ^? <g(C ₆₀ ^2? ) < <g(C ₆₀ ^3? ) <g(C ₆₀ ^5? )) indicating largest contributions from spin-orbit coupling for the monoanion. No diamagnetic states for the dianions of [60]- and [70]- fullerenes could be found so far but biradical species with largest zero field splittingsD=2.7 mT (C ₆₀ ^2? ), andD=3.1 mT (C ₇₀ ^2? ), respectively. The cation formation of C₆₀ (g=2.0023-2.0029; ΔB=0.15-0.20 mT) with antimony pentachloride was controlled by mass spectrometry. Stable cations were found only in methylenechloride. In other solvents like toluene addition reactions seem to occur.