Doppler-free optoacoustic spectroscopy

The first observation of Doppler-free optoacoustic spectroscopy is reported. As a first example the P (193) line of the 11-0 band of the B←X transition of ¹²⁷I₂ is used. The output of cw single mode dye laser is split into two equal intensity beams chopped at frequencies ω₁ and ω₂. The nonlinear compoment of the optoacoustic signal at the frequency (ω₁ + ω₂) is detected and Doppler-free resolution is obtained. Comparing the Doppler-free optoacoustic and fluorescence spectra of iodine measured under similar conditions, good agreement is found. Since optoacoustic and fluorescence methods complement each other, this opens up new possibilities for weakly or nonfluorescing molecules.     

Coercivity analysis in R17Fe83−χBχ magnets

We studied the coercivity in magnets of composition R₁₇Fe_83−χB_χ (R = Nd, Pr and χ = 8, 30), using measurements of the coercive field H_c, its angular dependence, and the magnetic viscosity coefficient S_v, for temperatures between 4.2 and 500 K. The results are discussed in relation to a model which does not specifically consider the detailed mechanisms involved in magnetization reversal, but which provides information about the magnetic properties in the activation volume v where magnetization reversal is initiated. It is concluded that the ordering temperature in v tends to be slightly smaller than in the bulk and that the room temperature anisotropy in v is not strongly reduced with respect to the bulk value. Finally, a direct evaluation of the dipolar interactions is in good agreement with results obtained from H_c(T).     

An FTIR study of the bonding of methoxy on Ni(100): effects of coadsorbed sulfur, carbon monoxide and hydrogen

The vibrational spectra of CH₃O_(a), CD₃O_(a), CDH₂O_(a) and CD₂HO_(a) on Ni(100) are analyzed and interpreted in terms of resonances between fundamental modes and either combinations or overtones. Analysis of the symmetry of the modes observed suggests that methoxy binds normal to the surface with C_s symmetry, at least at low coverages. Two distinct vibrational bands emerge in the vibrational spectrum of methoxy in the v(CO) region as the coverage increases which are attributed to bonding in four-fold hollow sites and bridging sites. These bands exhibit blue shifts of about 25 cm⁻¹ with increasing coverage up to the saturation coverage. The vibrational bands in the v(CH) region appear concomitantly at all coverages and shift down 12 cm⁻¹ as the coverage is increased. These shifts are attributed to changes in the metal-oxygen bond which are reflected in changes in the strength of the C---O and C---H bonds. Affects on the bonding also appear to occur with the coadsorption of hydrogen or CO with methoxy. Coadsorption of 0.36 ML hydrogen with 0.04 ML methoxy induces blue shifts of 15 and 7 cm⁻¹ for the v(CO) bands at 949 and 984 cm⁻¹, respectively. Adsorbing 0.43 ML of CO with 0.04 ML methoxy (and 0.04 ML hydrogen) causes a red shift of 20 and 12 cm⁻¹ for these bands. A drastic drop in mode intensities for methoxy when CO is coadsorbed suggests that the methoxy tilts away from the surface normal. Pre-adsorbing sulfur on the Ni(100) surface reduces the amount of methoxy formed from methanol, but the v(CO) methoxy bands are unshifted in frequencies relative to their position for the same methoxy coverage on the clean surface.     

Noncritical vectorial phase matchings in nonlinear optics of crystals and infrared up-conversion

The exact analytic expressions for the vectorial group phase matching (PM) conditions have been obtained for sum and difference frequency generation processes ω₃ = ω₁ ± ω₂ (ω₃= ω₂ − ω₁) in nonlinear anisotropy crystals, which ensure a wide-band conversion of signals (ω₂) and images. The tangential PM conditions for all possible interaction types in the negative and positive uniaxial crystals have been studied. Scanning of the frequency of vectorial group PM has been studied by examples of LiNbO₃, LiIO, and HgGa₂S₄ crystals when changing the pump direction or pump frequency ω₁. The possibility of tuning the wide-band operation all over the transparency region of the LiIO₃, crystal has been shown. The double noncriticality conditions of PM in frequency cd; and acceptance angle have been studied and the possibility of their realization in a near and middle infrared region (IR) has been shown. A generalization of consideration to the other types of noncritical PMs (including multiples ones), has been made, including at an angle 90° between the propagation directions of waves with frequencies ω₁ (1) and ω₂ (2). The method of definition of the spectral bandwidths and acceptance angles of critical and noncritical PM taking into account the concordant change in the propagation angles of waves 1 and 2 has been proposed.     

A comparison of the zero bias differential resistance of Ag:Nb and Ag:Nd1.85Ce0.15CuO4−δ point contacts as a function of temperature below Tc

Point contact spectra for contacts between Ag and two different superconductors, Nb and Nd_1.85Ce_0.15CuO_4−δ, were measured as a function of temperature using a crossed wire-wedge technique (R.C. Reinertson et al., Physica B 165&166 (1990) 1615). The temperature dependence of the zero bias resistance quantitatively agrees with predictions of the theory by Blonder, Tinkham and Klapwijk (Phys. Rev. B 25 (1982) 4515) for normal:superconductor point contacts for all interface scattering barrier strengths observed in this study (Z = 0.3 to Z = 1.0). The zero bias temperature dependence of Ag:Nd_1.85Ce_0.15CuO_4−δ contacts indicates a systematically higher range of barrier strengths and contact resistances than typical Ag:Nb contacts.     

IR-spectra of (CO2)2 dimers and collision-induced absorption of carbon dioxide in the region of the fermi doublet (ν1, 2ν2)

The positions and intensities of all vibrational transitions in the (ν₁, 2ν₂) Fermi doublet region of (CO₂)₂ dimers are obtained by means of variational method. The collision-induced absorption in compressed carbon dioxide is shown to be mainly due to dimeric absorption. Assignment of ν₁ and 2ν₂ vibrational bands in isolated CO₂ molecule is performed by consideration of the symmetries and intensities of dimeric vibrations.     

A role of solvent in vibrational energy relaxation of metalloporphyrins

The formation of a vibrationally excited photoproduct of metalloporphyrins upon (π, π*) excitation and its subsequent vibrational energy relaxation were monitored by picosecond time-resolved resonance Raman spectroscopy. Stokes Raman bands due to a photoproduct of nickel octaethylporphyrin (NiOEP) instantaneously appeared upon the photoexcitation. Their intensities decayed with a time constant of 300 ps, which indicates electronic relaxation from the (d, d) excited state (B_1g) to the ground state (A_1g), being consistent with the results of transient absorption measurements by Holten and coworkers. Anti-Stokes ν₄ and ν₇ bands for vibrationally excited (d, d) state of NiOEP decayed with time constants of 10 and 300 ps. The former is ascribed to vibrational relaxation, while the latter corresponds to the electronic relaxation from the (d, d) excited state to the electronic ground state. While the rise of anti-Stokes ν₄ intensity was instrument-limited, the rise of anti-Stokes ν₇ intensity was delayed by 2.6±0.5 ps, which indicates that intramolecular vibrational energy redistribution has not been completed in subpicosecond time regime. To study a mechanism of intermolecular energy transfer, solvent dependence of the time constants of anti-Stokes kinetics was investigated using various solvents. No significant solvent dependence of the rise and decay constants was observed for NiOEP. For an iron porphyrin, we observed two phases in intermolecular energy transfer. The fast phase was insensitive to solvent and the slow phase depended on solvents. A model of classical thermal diffusion qualitatively reproduced this behavior. For solute-solvent energy transfer process, low-frequency modes of proteins seem to be less important.     

Low-temperature AC conductivity of Bi2Sr2CaCu2O8+δ

We report measurements of anamolously large dissipative conductivities, σ₁, in Bi₂Sr₂CaCu₂O_8+δ at low temperatures. We have measured the complex conductivity of Bi₂Sr₂CaCu₂O_8+δ thin films at 100–600 GHz as a function of doping from the underdoped to the overdoped state. At low temperatures there exists a residual σ₁ which scales with the T=0 superfluid density as the doping is varied. This residual σ₁ is larger than the possible contribution to σ₁ from a thermal population of quasiparticles (QP) at the d-wave gap nodes.     

Experimental and theoretical 31P and 77Se nuclear magnetic shielding tensors for bis(dineopentoxyphosphorothioyl) diselenide

An intergrown crystal of two phases of bis(dineopentoxyphosphorothioyl) diselenide 1 was investigated by goniometer ³¹P NMR. From the angular dependence of the chemical shift, the tensors of a triclinic and a monoclinic phase were determined. The principal values σ₁₁, σ₂₂, and σ₃₃ of the absolute nuclear magnetic shielding tensors for the triclinic phase are 134.1, 227.2, and 375.5 ppm and for the monoclinic phase are 132.4, 227.8, and 374.2 ppm, respectively. In both cases, the principal axis 3 of the ³¹P tensor is directed nearly along the P=S bond and the principal axis 2 is nearly perpendicular to the S=P—Se plane. Calculations of the ³¹P and ⁷⁷Se nuclear magnetic shielding tensors were performed for molecules of both phases of 1 and for model compounds by the sum-over-states density functional perturbation theory IGLO method. The rms distances between calculated and experimental ³¹P NMR icosahedral tensor values σ_j(j = 1,…,6) amount to 17–21 ppm. The calculated and experimental orientations of the ³¹P principal axes show a maximum difference of 5° and rms distances of 3.2 and 3.3°. For the principal value σ₃₃ of the selenium shielding tensor the agreement between calculated and experimental values is satisfactory, but the calculated values σ₁₁ and σ₂₂ are distinctly too small. Calculations for a model compound in which the methyl groups of the neopentoxy residue are substituted by protons lead practically to the same results.     

Quantum-resolved angular distributions of neutral products in electron-stimulated processes: desorption of CO from Pt(111)

The first quantum-resolved angular distribution measurements of electronically-excited neutral molecules which have undergone electron stimulated desorption (ESD) are presented. Two-dimensional imaging of laser resonance-enhanced multiphoton ionization (REMPI) is used to obtain angular distributions of CO^* in the v=0 vibrational level of the metastable a³Π_r state desorbed from CO/Pt(111) by 350 eV electrons. For saturation CO coverages at 90 K, sharp Gaussian distributions peaked about the surface normal (6° ± 0.5° half-width at half maximum) are observed, consistent with previously reported data acquired by ESDIAD (ESD ion angular distributions). The (1 + 1) photon REMPI scheme for state-specific CO^* detection involves the b³Σ(v = 0) ← a³Π(v = 0) transition at 283 nm, followed by photoionization at the same wavelength. In this paper, the overall experimental technique for REMPI imaging of products from electron stimulated processes is discussed. Thus specific CO^* data as a function of coverage and temperature is presented for comparison with the ESDIAD results.     

Landau damping in degenerate solid state plasmas

Helicon waves are found useful for studying Landau damping in degenerate plasmas. The damping is analyzed as the phase velocity of the wave is increased from ω/q v_F to ω/q v_F. There is no first-orderlike transition at ω/q = V_F. In the collisionless limit, the damping tends to zero as ω/q → v_F. For finite collision times τ it does not vanish for ω/q > v_F. Nonlocal corrections to the wavelength exhibit a peak at ω/q = V_F, which degenerates into a shoulder for ωτ 100.     

Phase transitions and electrical properties of CsH(SO4)0.76(SeO4)0.24 mixed crystals

The study by X-ray diffraction, calorimetry, vibrational and impedance spectroscopy of CsH(SO₄)_0.76(SeO₄)_0.24 new solid solution is presented. Crystals of this composition undergo two phase transitions at T = 333 and 408 K. The last one at 408 K is a superionic-protonic transition (SPT) related to a rapid [HS(Se)O₄⁻] reorientation and fast H⁺ diffusion. A sudden jump in the conductivity plot confirms the presence of this transition. Above 408 K, this high temperature phase is characterized by high electrical conductivity (7 × 10^t-3 Ω⁻ cm⁻¹) and low activation energy (E_a < 0.3 eV).     

Observations of ω0/2 harmonic emission from 0.35μm laser-irradiated plasmas

Observations of ω₀/2 harmonic emission from both spherical and plane targets irradiated by 0.35 μm, 800 ps laser pulses have been obtained with simultaneous high spectral and temporal resolutions of 16 Å and 20 ps respectively. The ω₀/2 harmonic emission spectrum is interpreted as providing a direct measurement of the frequency of the ω₀/2 plasma waves and hence can be used to estimate the electron temperature.     

钙钛矿(C6H5CH2NH3)2PbBr4拉曼光谱研究

运用激光拉曼光谱实验和密度泛函理论计算研究了450～1 700 cm-1光谱范围内有机-无机杂化钙钛矿材料(C₆H₅CH₂NH₃)₂PbBr₄的振动模式特性。对比实验所得拉曼光谱和理论计算所得拉曼光谱,发现密度泛函理论计算可以很好的模拟(C₆H₅CH₂NH₃)₂PbBr₄有机部分的分子振动模式。同时通过比较分析密度泛函理论计算和参考文献,对450～1 700 cm-1光谱范围内的拉曼峰的分子振动模式进行了初步的归属,并发现该光谱范围内的拉曼峰主要是由(C₆H₅CH₂NH₃)₂PbBr₄分子中有机部分振动所产生的。     

Simplified models for vibrational energy transfer in proteins

We consider the transfer of vibrational energy in proteins and derive a simplified model for the resonant energy exchange between different vibrational modes. We use the parameters of an earlier study [K. Moritsugu, et al., Phys. Rev. Lett. 85 (2000) 3970 ] to compare our predictions with the results of the molecular dynamics simulations, and reveal an excellent agreement.     

Measurement of L X-ray production cross sections and Li subshell fluorescence yields

L_i (i=1, 2 and 3) X-ray production cross sections have been measured for 14 elements in the atomic number range 55≤Z≤81 at 15.73 keV. The values of L_i subshell fluorescence yields (ω₁, ω₂ and ω₃) have been determined using the presently measured X-ray production cross sections and the theoretical L_i subshell photoionization cross sections values, Coster–Kronig transition probabilities and radiative emission rates. The measured X-ray production (XRP) cross-sections and fluorescence yield values were compared with the theoretical and semi empirical values, respectively.     

Electron energy loss spectroscopy studies of nitrogen adsorption on W(100)

Vibrational excitations of nitrogen on W(100) are investigated over the 100–300 K temperature range using elastic and inelastic electron scattering. New vibrational modes of nitrogen are identified that require different mode assignments from previous work. Experimental evidence for a molecular precursor to the atomic β₂ phase of adsorbed nitrogen is presented. Coverage dependent studies of vibrational modes suggests conversion between two different molecular surface phases and between atomic and molecular phases. A new ordered nitrogen phase characterized by a (4 × 1) LEED pattern is observed. The new phase appears to consist of orthogonal domains of p(4 × 1) symmetry that contain atomic nitrogen at the four fold sites (the β₂ atomic phase) with additional bridge-bonded nitrogen atoms in the unit cell.     

A Raman study of the structural properties of YBa2(Cu1 − xFex)3Oy

The effects of Fe-substitution of YBa₂Cu₃O_y have been investigated by means of Raman scattering, X-ray diffraction, resistivity and susceptibility measurements. A series of samples of YBa₂(Cu_{1 − x}Fe_x)₃O_y with different dopant concentration (0 x 0.15) has been prepared in two batches, the second set having undergone twice the heat and mechanical treatment used to produce the first batch. Considerable improvement in the superconducting transition temperature, T_c, is obtained upon reprocessing. A phase transformation from orthorhombic to tetragonal symmetry is observed for x=0.05 from the X-ray measurements in agreement with previous work. Using a micro-Raman technique, all five A_g vibrational modes have been measured and their dependence on Fe-concentration is analyzed. There are indications that iron substitutes for copper at both sites and that the structure is a mixture of orthorhombic and tetragonal microdomains for all x.     

Normal skin effect in the polycrystals

The surface impedance γ and the penetration depth δ of the electromagnetic field was calculated for a polycrystalline conductor under the conditions of the normal skin effect. The polycrystal is composed from the single-phase slightly anisotropic single-crystalline grains of arbitrary symmetry. Corrections (γ-γ₀)/γ₀ and (δ-δ₀)/δ₀ due to the polycrystallinity are functions of the parameter ζ=δ₀/a, where γ₀ and δ₀ are the impedance and the penetration depth of the isotropic conductor with the conductivity σ₀=Sp σ_ik/3, σ_ik is the separate grain conductivity tensor, and a is the mean size of a grain.

The effective conductivity of a polycrystal can be obtained either from the impedance γ (σ_ef^(γ)) or from the penetration depth δ (σ_ef^(δ)) It was found that σ_ef^(γ)≠σ_ef^(δ) The corrections (σ-σ_ef^((γ))/σ₀ and (σ₀-σ_ef^(δ))/σ₀ depend on the frequency of the incident wave.

The obtained results are also applicable in the infrared spectrum region. It was shown that, just as for the isotropic conductor, there is the total reflection of the electromagnetic wave from the polycrystal surface.

It was necessary to examine the oblique incidence of an electromagnetic wave onto the surface of an isotropic metal for the substantiation of the set of the boundary conditions used.