The effect of an anti-hydrogen bond on Fermi resonance:A Raman spectroscopic study of the Fermi doublet ν1-ν12 of liquid pyridine

The effects of an anti-hydrogen bond on the ν1-ν12 Fermi resonance(FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy.Three systems,pyridine/water,pyridine/formamide,and pyridine/carbon tetrachloride,provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex.Water forms a stronger anti-hydrogen bond with pyridine than with formamide,and in the case of adding non-polar solvent carbon tetrachloride,which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine,the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce.The dilution studies are performed on the three systems.Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode ν1 and triangle mode ν12 of pyridine at different volume concentrations,which are calculated according to the Bertran equations,in three systems,we find that the solution with the strongest anti-hydrogen bond,water,shows the fastest change in the ν1-ν12 Fermi coupling coefficient W with the volume concentration varying,followed by the formamide and carbon tetrachloride solutions.These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν1-ν12 FR of pyridine.According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory,a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν1-ν12 FR of pyridine is given.     

The effect of an anti-hydrogen bond on Fermi resonance： A Raman spectroscopic study of the Fermi doublet v1-v12 of liquid pyridine

The effects of an anti-hydrogen bond on the v1 v12 Fermi resonance （FR） of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, and pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming a hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of the Fermi coupling coefficient W of the ring breathing mode v1 and triangle mode v12 of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the v1-v12 Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the v1-v12 FR of pyridine. According to the mechanism of the formation of an anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the v1 - v12 FR of pyridine is given.     

HIGH-RESOLUTION ANALYSIS OF THE ν2+2ν3 BAND OF HDO

The Fourier transform spectrum of the ν₂+2ν₃ band of the HDO molecule was recorded with a resolution of 0.02 cm^-1. The spectrum was rotational analysed and the spectroscopic parameters of the (0,1,2) state were estimated in terms of Watson's effective rotational Hamiltonian model and also the model in the Padé-Borel approximation form. They reproduce the upper energy levels with an accuracy close to the experimental uncertainty of 0.001 cm^-1.     

Simulation of near-infrared photodiode detectors based on β-FeSi2/4H-SiC heterojunction

In this paper, we propose the near-infrared p-type β-FeSi₂/n-type 4H-SiC heterojunction photodetector with semiconducting silicide (β-FeSi₂) as the active region for the first time. Optoelectronic characteristics of the photodetector are simulated using a commercial simulator at room temperature. The results show that the photodetector has a good rectifying character and a good response to the near-infrared light. Interface states should be minimized to obtain a lower reverse leakage current. The response spectrum of the β-FeSi₂/4H-SiC detector, which consists of a p-type β-FeSi₂ absorption layer with a doping concentration of 1×10¹⁵ cm^-3 and a thickness of 2.5 μm, has a peak of 755 mA/W at 1.42 μm. The illumination of the SiC side obtains a higher responsivity than that of the β-FeSi₂ side. The results illustrate that the β-FeSi₂/4H-SiC heterojunction can be used as a near-infrared photodetector compatible with near-infrared optically-activated SiC-based power switching devices.     

Development and characteristic analysis of a field-plated Al2O3/AlInN/GaN MOS–HEMT

We present an AlInN/AlN/GaN MOS–HEMT with a 3 nm ultra-thin atomic layer deposition (ALD) Al₂O₃ dielectric layer and a 0.3 μm field-plate (FP)-MOS--HEMT. Compared with a conventional AlInN/AlN/GaN HEMT (HEMT) with the same dimensions, a FP-MOS--HEMT with a 0.6 μm gate length exhibits an improved maximum drain current of 1141 mA/mm, an improved peak extrinsic transconductance of 325 mS/mm and effective suppression of gate leakage in both the reverse direction (by about one order of magnitude) and the forward direction (by more than two orders of magnitude). Moreover, the peak extrinsic transconductance of the FP-MOS--HEMT is slightly larger than that of the HEMT, indicating an exciting improvement of transconductance performance. The sharp transition from depletion to accumulation in the capacitance--voltage (C--V) curve of the FP-MOS--HEMT demonstrates a high-quality interface of Al₂O₃/AlInN. In addition, a large off-state breakdown voltage of 133 V, a high field-plate efficiency of 170 V/μ m and a negligible double-pulse current collapse is achieved in the FP-MOS--HEMT. This is attributed to the adoption of an ultra-thin Al₂O₃ gate dielectric and also of a field-plate on the dielectric of an appropriate thickness. The results show a great potential application of the ultra-thin ALD-Al₂O₃ FP-MOS--HEMT to deliver high currents and power densities in high power microwave technologies.     

一氧化二氮分子位于775 nm的6υ3振动泛频跃迁的高精密光腔衰荡光谱

Transitions of the 6υ₃ overtone band of ¹⁴N₂ ¹⁶O near 775 nm have been studied by continuous-wave cavity ring-down spectroscopy. Line positions and intensities were derived from a fit of the line shape using a hard-collisional profile. The line positions determined with absolute accuracy of 5×10^-4 cm^-1 allowed us to reveal finer ro-vibrational couplings taking place after J>14 except a strong anharmonic interaction identified by the effective Hamiltonian model. The absolute line intensities have also been retrieved with an estimated accuracy of 2% for a majority of the unblended lines. A new set of ro-vibrational and dipole moment parameters were derived from the experimental values. A comparison between the line positions and intensities of the 6υ₃ band obtained in this work and those from previous studies is given.     

The instability conditions of a gas trapped in weak weakly interacting Fermi magnetic field

In this paper the analytical expression of free energy expressed by small parameter r of a weakly interacting Fermi gas trapped in weak magnetic field is derived by using `the maximum approximation' method and the ensemble theory. Based on the derived expression, the exact instability conditions of a weakly interacting Fermi gas trapped in weak magnetic field at both high and low temperatures are given. From the instability conditions we get the following two results. (1) At the whole low-temperature extent, whether the interactions are repulsive or attractive with (ɑn + 4\varepsilon_F/3) (n and \varepsilon _F denote the particle-number density and the Fermi energy respectively, ɑ= 4π a\hbar_F/ m, and a is s-wave scattering length) positive, there is a lower-limit magnetic field of instability; in addition, there is an upper-limit magnetic field for the system of attractive interactions with (ɑ n + \varepsilon_F/3) negative. (2) At the whole high-temperature extent, the system with repulsive interactions is always stable, but for the system with attractive interactions, the greater the scattering length of attractive interactions | a | is, the stronger the magnetic field is and the larger the particle-number density is, the bigger the possibility of instability in the system will be.     

POSITRON LIFETIME STUDIES OF Y1-xCaxBa2Cu3O7-δ AND Y1-xCaxBa2Cu3-xFexO7-δ

In this paper it is reported that the measurement of the bulk positron lifetime as a function of substitution content x in the temperature range from 70 to 220K was performed in two high-T_c superconducting systems, Y_1-xCa_xBa₂Cu_3-xFe_xO_7-δ and Y_1-xCa_xBa₂Cu₃O_7-δ. It was found that τ_B of both systems decreases significantly with x and the temperature dependence of τ_B is very weak in normal state. In lower temperature region (Tc), a dramatic x-dependent temperature variation of τ_B was observed in the Ca-substituted system: from a decrease of τ_B with decreasing T to an increase of τ_B. With increasing x, the temperature dependence of τ_B remains weak in the Ca- and Fe- substituted systems. Compared with the experimental data of positron lifetime in other substituted systems and the calculation of the positron density distribution, the authors suggest that positron bulk lifetime spectra behaviour can be interpreted by the physical model based on the transfer of electron density between the CuO₂ planes and Cu-O chains. Therefore, the study of positron lifetime spectra provides a useful means to detect the local charge density and to study the correlation between the electronic structure and the high-T_c superconductivity.     

Low temperature laser absorption spectra of methane in the near-infrared at 1.65 μm for lower state energy determination

Direct absorption spectra of the 2v₃ band of methane (CH₄) from 6038 to 6050 cm^-1 were studied at different low temperatures using a newly developed cryogenic cell in combination with a distributed feedback (DFB) diode laser. The cryogenic cell can operate at any stabilized temperature ranging from room temperature down to 100 K with temperature fluctuation less than ±1 K within 1 hour. In the present work, the CH₄ spectra in the range of 6038-6050 cm^-1 were recorded at 296, 266, 248, 223, 198, and 176 K. The lower state energy E″ and the rotational assignment of the angular momentum J were determined by a “2-low-temperature spectra method” using the spectra recorded at 198 and 176 K. The results were compared with the data from the GOSAT and the recently reported results from Campargue and co-workers using two spectra measured at room temperature and 81 K. We demonstrated that the use of a 2-low-temperature spectra method permits one to complete the E″ and J values missed in the previous studies.     

Intrinsic tunneling study of underdoped Bi2Sr2-xLaxCuO6+δ superconductors

We report on a tunneling study of underdoped submicron Bi₂Sr_2-xLa_xCuO_6+δ (La-Bi2201) intrinsic Josephson junctions (IJJs), whose self-heating is sufficiently suppressed. The tunneling spectra are measured from 4.2 K up to the pseudogap opening temperature of T^* = 260 K. The gap value found from the spectral peak position is about 35 meV and has a weak temperature dependence both below and above the superconducting transition temperature of T_c = 29 K. Since the superconducting gap should have a value of 10-15 meV, our results indicate that the pseudogap (～35 meV) plays an important role in the underdoped La-Bi2201 intrinsic tunneling spectroscopy down to the lowest temperature of 4.2 K. However, the contribution of the superconducting gap can be separated by normalizing the spectra to the one near and above T_c, which shows that the IJJs can be a useful tool for the study of the electronic properties of the La-Bi2201 cuprate superconductors.     

Study of asymmetric wavenumber shift of the Fermi doublet ν1 − 2ν2 in the Raman spectrum of liquid carbon disulfide

The Raman spectra of liquid carbon disulfide (CS₂) diluted with benzene (C₆H₆) have been measured. By changing the CS₂, the concentration, we found an asymmetric wavenumber shift phenomenon. With decreasing concentration of CS₂, the position of the ν₁ (655 cm⁻¹) band remains practically unchanged, and the 2ν₂ (796 cm⁻¹) band shifts toward higher wavenumbers. To interpret this asymmetric wavenumber shift phenomenon of the Fermi doublet ν₁ − 2ν₂ in the Raman spectra satisfactorily, we propose a modified Bertran model. The values of the Fermi resonance (FR) parameters of CS₂ at different concentrations were calculated using the Bertran equations. In addition, we found the fundamental ν₂, which should be independent of the FR interaction, shifted to higher wavenumbers as the concentration decreased. This shift was probably driven by the tuning of the FR. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of pressure effect on Fermi resonance in binary solution

The Fermi resonance behaviours of the two groups of binary solutions --- pyridine and methanol, benzene and carbon tetrachloride, under different pressures are investigated according to their Raman spectra. The effect of pressure on Fermi resonance in binary solution differs significantly from that in pure liquid. In a binary solution, with the intermolecular distance shortening, the intermolecular interaction potential increases, the shift rates of the Raman spectral lines increase, the spectral line splitting occurs ahead of that in pure liquid, and the wavenumber separation Δ₀ between the unperturbed harmonic levels shifts more quickly, too. The Fermi resonance parameters, the coupling coefficient W and the intensity ratio R of the two Raman bands, decrease rapidly with pressure increasing, and the pressure at which Fermi resonance phenomenon disappears is much lower than that in pure liquid, especially in the solution whose molecules are of the same polarity. This article is valuable in the identification and the assignment of spectral lines under high pressure, as well as the study of high pressure effect, intermolecular interaction, and solvent effects in different cases, etc.     

Absorption spectrum of the (CF4) dimer in liquid argon solution

The concentration dependence of the shape of absorption bands in the spectrum of CF₄ in liquid argon is studied in the concentration range (0.01–17)×10^?3 molar fractions at 93 K. In all spectral regions related to ν₃, the shape of the spectral function is determined, along with the Fermi resonance 〈ν_i,ν₃+1,ν₄|≈〈νi,ν₃,ν ₄+2|, by the resonance dipole-dipole interaction. In the spectral region of the Fermi doublet ν ₁+ν₃≈ ν₁+2ν₄, the spectrum of the contact (CF₄)₂ dimer is identified. Agreement between this spectrum and the calculated spectrum is achieved by simultaneously taking intramolecular and intermolecular resonances into account. The distance R _C-C in the dimer is 4.85(15) Å. The calculations of the spectra of (¹²CF₄)₂ and (¹³CF₄?¹²CF₄) dimers with this value of R _C-C in the region ν ₃≈2ν₄ agree with the experiment.     

Analysis of the ν 3, ν 6, ν7 + ν 8 Fermi and Coriolis interacting band system in methyl cyanide

A reinvestigation of the Fermi and Coriolis interacting band system ν ₃, ν ₆, ν ₇ + ν ₈ of methyl cyanide has been performed with a resolution better than 0·3 cm^-1. The observed J structure in some of the K sub-bands enables an unambiguous numbering of the sub-band Q branches to be made. The resulting assignment, which differs from Amat and Nielsen's previous assignment, is used to re-analyse the band system. A band contour has been calculated by computer simulation, including the effects of both the Fermi resonance of ν ₆ with ν ₇ + ν ₈ and the Coriolis resonance of ν ₆ with ν ₃; both the frequency and intensity perturbations which result have been accurately reproduced. The molecular parameters obtained from our analysis are summarized in table 2.     

Raman spectroscopy study of the Fermi resonance between a local vibration and the two‐phonon spectrum in PbI2 crystal

The problem of complex Fermi resonance (FR) involving a local vibration is considered. It is shown for the first time that in the PbI₂ crystal, owing to the features of phonon bands, the following two effects superpose on each other: (1) the traditional FR between the fundamental Ω(A_1g) vibration and the two‐phonon states (TPS) arising from the 2Ω(E_u) vibrations, and (2) the FR between the impurity vibration and the same TPS band. It is shown theoretically that in the case of such complex FR the shape of the spectrum strongly depends on the impurity concentration, anharmonic constants and the phonon band structure. An analysis of experimental data and comparison with theory is made. Copyright © 2008 John Wiley & Sons, Ltd.     

Fermi resonance in the spectrum of deuterated monofluoroacetylene

A strong Fermi resonance interaction between two Σ-type levels ν₂ and 2ν₃ of DCCF together with the corresponding resonance between the levels ν₂ + ν₃ and 3ν₃ has been observed. The rotational structure of the bands has been investigated in both the diads which are situated around 2100 and 3100 cm^?1. The molecular constants involved have been derived.     

Calculation of the charge transfer transition energy of the mesitylene–ICl complex by ab initio and TDDFT methods: Comparison with other methylbenzene–ICl complexes

Of the four plausible isomeric structures of the mesitylene–ICl charge transfer (CT) complex, the most feasible one was determined by a detailed ab initio and DFT study at the HF, B3LYP and MPW1PW91 levels using the 6-31++G(d,p) basis set. Potential energy surface scans followed by frequency calculation and full optimization revealed that the I–Cl bond, with its I atom oriented towards the aromatic ring, stands vertically above an unsubstituted C-atom, being inclined at about 6° to the C ₃-axis. Complexation increases the I–Cl bond length. Correction for basis set superposition error through a counterpoise calculation yields a binding energy close to the experimental value. The electronic CT transition energy (hν _CT) with this ground-state structure as input was calculated in vacuo by the CIS method and in carbon tetrachloride medium by the TDDFT method under the polarizable continuum model. In a similar way the values of hν _CT were calculated for complexes of ICl with p-xylene, durene and hexamethylbenzene. Throughout the series of methylbenzene complexes, the TDDFT-calculated values of hν _CT were less than the experimental values and such underestimation may be attributed to the inherent difficulties of DFT to take into account long-range interactions. However, the trend of the variation of hν _CT with the number and position of methyl groups in the series was reasonably similar to the trend followed by the experimental CT transition energies.     

Bi2Te3-xSex(x≤3)同晶化合物电子结构的第一性原理研究

本文采用基于密度泛函理论的第一性原理全势能线性缀加平面波方法(FLAPW),分析了Bi₂Te_3-xSe_x体系中各原子自旋轨道耦合(SOI)的p_1/2修正对体系性质的影响,并对Bi₂Te_3-xSe_x(x≤3)同晶化合物的电子特性进行系统的理论研究,首次计算出Bi₂S 关键词： 2Te_3-xSe_x(x≤3)同晶化合物')" href="#">Bi₂Te_3-xSe_x(x≤3)同晶化合物 第一性原理 电子结构 自旋轨道耦合     

分子费米共振拉曼光谱强度分析

测量了CCl₄和CS₂分子的Raman光谱。用Bertran理论和群论等相关理论对其光谱强度进行了分析,获得了发生费米共振分子的拉曼光谱强度的特殊规律： (1)发生费米共振的基频和倍频(和频)间发生能量转移,两光谱强度大小相互接近,当发生费米共振的基频和倍频(和频)间距离很小时,两发生费米共振的光谱强度相等(R=1);(2)能出现倍频光谱强度高于其基频光谱强度;(3)也会观测到费米共振光谱,而观测不到参与费米共振的和频中的基频光谱。此研究对化学、材料科学中的分子结构、材料成分等研究中的谱线认证、归属有很好的参考价值。