用受激拉曼泵浦方法高效制备v=2振动激发态氘分子

We report the preparation of D₂ molecules in v=2 level in molecular beam condition. A single longitudinal mode laser system was used for excitation of D₂ from (v=0, j=0) to (v=2, j=0) with the scheme of stimulated Raman pumping. An excitation efficiency of 25.2% has been achieved, which was determined by the scheme of resonance-enhanced multiphoton ionization. Dependence of relative excitation efficiency on laser energy has been measured. We found that the increasing rate of excitation efficiency became slower as pulse energy of Stokes laser increase, while the excitation efficiency still increases approximately linearly with pump pulse energies up to 60 mJ. The spectral line shapes of Raman transition was also measured at different laser energies and considerable dynamical Stark effect was observed. A single peak was found on the three dimension surface of relative excitation efficiency, indicating the process occurred in the present study is a process of stimulated Raman pumping instead of stimulated adiabatic Raman passage.     

High‐resolution stimulated Raman study of the first vibrational hot band of 14N2. Separate observation of the spectra of the ortho and para species.

We present high‐resolution stimulated Raman spectra of the first hot band of nitrogen, ¹⁴N₂, obtained under conditions of low sample pressure and temperature. The use of a Raman optical pumping system allowed us to transfer a significant amount of population to the v = 1 vibrational state, which made possible the observation of the aforementioned hot band with good S/N ratio without resorting to the use of high temperatures or pressures. This has resulted in a more precise and accurate determination of the peak positions than previously existing ones, which in turn has yielded improved values for the molecular constants obtained from the analysis. The rotational selectivity of the pumping process (only one rotational state is initially populated in v = 1), coupled with the negligible probability of nuclear spin interconversion in the time frame of the experiment, has allowed us to observe the hot band spectra of the ortho and para species of ¹⁴N₂ separately. Copyright © 2013 John Wiley & Sons, Ltd.     

The millimeter-wave rotational spectrum of fluorobenzene

The room-temperature rotational spectrum of fluorobenzene was studied in the frequency region 167-318 GHz. Rotational transitions were assigned and measured in the ground vibrational state, and all six excited vibrational states with energies below 600 cm⁻¹, i.e., v₁₁ = 1, v₁₁ = 2, v_18b = 1, v_16a = 1, v_16b = 1, and v_6a = 1. Accurate quartic-level spectroscopic constants were determined for all states, allowing spectral predictions well into the submillimeter region. The states v_18b = 1 and v_16a = 1 were found to be connected by a strong Coriolis interaction, which allowed precise determination of their energy separation, ΔE = 7.455088(3) cm⁻¹. Unambiguous assignment of vibrational modes was made on the basis of the calculated inertial defect and nuclear spin statistical weights. Rotational constants for the ¹³C₄ isotopomer have also been redetermined and two new least-squares determinations of the geometry of fluorobenzene, r₀ and are reported.     

BiFeO3 ceramic matrix with Bi2O3 or PbO added: Mössbauer, Raman and dielectric spectroscopy studies

In this paper Mössbauer, Raman and dielectric spectroscopy studies of BiFeO₃ (BFO) ceramic matrix with 3 or 10 wt% of Bi₂O₃ or PbO added, obtained through a new procedure based on the solid-state method, are presented. Mössbauer spectroscopy shows the presence of a single magnetically ordered phase with a hyperfine magnetic field of 50 T. Raman spectra of BFO over the frequency range of 100-900 cm⁻¹ have been investigated, at room temperature, under the excitation of 632.8 nm wavelength in order to evaluate the effect of additives on the structure of the ceramic matrix. Detailed studies of the dielectric properties of BiFeO₃ ceramic matrix like capacitance (C), dielectric permittivity (ε) and dielectric loss (tan δ), were investigated in a wide frequency range (1 Hz-1 MHz), and in a temperature range (303-373 K). The complex impedance spectroscopy (CIS) technique, showed that these properties are strongly dependent on frequency, temperature and on the added level of impurity. The temperature coefficient of capacitance (TCC) of the samples was also evaluated. The study of the imaginary impedance (−Z″) and imaginary electric modulus (M″) as functions of frequency and temperature leads to the measurement of the activation energy (E_ac), which is directly linked to the relaxation process associated with the interfacial polarization effect in these samples.     

Laser desorption of NO from a thick C60 film

The desorption of NO molecules from a thick C₆₀ film is reported. A thermal desorption spectrum indicates two adsorption sites with binding energies of E_b = 0.30 eV and 0.55 eV. For laser desorption the fullerene surface is exposed to NO and excited by 7 ns UV laser pulses. Desorbing NO molecules are recorded state selectively as well as time resolved. The time-of-flight measurement indicates three different desorption pathways. A fast channel shows rovibronic temperatures of T_rot(v″ = 0) = 370 K, T_rot(v″ = 1) = 390 K and T_vib = 610 K as well as strong rotational-translational coupling. The desorption yield for the fast channel increases linearly with pulse energy with a desorption cross section of σ = (5.1 ± 0.9) × 10⁻¹⁷ cm². Dominating the signal for small J″ values is a slow channel with low rotational and translational temperatures of about 110 K. We assign this peak to a laser-induced thermal desorption. For large pump-probe delays the data deviate from the Maxwellian flux distribution and a third channel appears with extremely late arrival times.     

Interactions between vibrational polyads of propyne, H3CCCH: Rotational and rovibrational spectroscopy of the levels around 1000 cm

The study of vibration resonance physics in propyne is based on experimental measurements of about 600 new rotational transitions between 495-590 and 700-760 GHz in excited vibrational levels v₅ = 1, v₈ = 1, v₁₀ = 3 and v₉ = v₁₀ = 1 with vibrational energies around 1000 cm⁻¹. The limits to the assignments and analysis were imposed by as yet unresolved anharmonic resonances with the states of the next higher polyad of levels lying above 1200 cm⁻¹, which affect the rotational states involved in transitions that would be measurable with non-vanishing intensities. Vibration-rotation spectra pertaining to the levels in question were studied in the regions 880-1150 cm⁻¹ (the ν₅ and ν₈ fundamental bands), 550-750 cm⁻¹ (the v₉ = v₁₀ = 1 ← v₁₀ = 1 hot bands) and 250-400 cm⁻¹ (the v₁₀ = 3 ← v₁₀ = 2 “superhot” bands). A simultaneous least-squares fit of both types of data provides their reliable but in the case of accurate rotational data not always fully quantitative reproduction.     

High-resolution laser spectroscopy of the potassium-argon molecule: The BΣ state

The absorption spectrum of the KAr molecule has been observed with high resolution between 13 032 and 13 077 cm⁻¹ using tunable laser diodes as light sources, a supersonic beam for production of the molecules, and laser-induced fluorescence for detection. In addition, optical-optical double resonance (OODR) experiments have been performed to simplify the spectrum and to get rotational assignment. Altogether, 670 lines due to the transition B²Σ⁺ ← X²Σ⁺ have successfully been assigned with vibrational levels of the B state ranging from v = 0 to v = 6. The corresponding energy values were fitted to the well-known Dunham expansion. In addition, we were able to analyse a local perturbation between the vibrational level v = 1 of the B state and v = 14 of the A²Π_3/2 state. Unexpected extra lines in the OODR spectra are most probably due to a collision-induced population of other levels. For the equilibrium distance and the well-depth of the B state we obtain from the Dunham expansion 7.03 (8) Å and 26.2 (8) cm⁻¹, respectively.     

Coherent Raman spectra of the ν1 mode of BF3 and BF3

High resolution (0.001 cm⁻¹) coherent anti-Stokes Raman spectroscopy (CARS) was used to directly examine the ν₁ symmetric stretching mode of the planar symmetric D_3h molecules ¹⁰BF₃ and ¹¹BF₃. Simulations of the spectra were done using ν₁ rovibrational parameters deduced from published infrared hot-band and difference-band studies and the close similarity to the observed CARS spectra confirms the validity of the infrared constants. No significant perturbations by Fermi resonance or Coriolis interactions with nearby states are observed, in marked contrast to the case of sulfur trioxide, a similar D_3h molecule recently studied. In the harmonic approximation, the ¹⁰BF₃ and ¹¹BF₃ν₁ Q-branches would be identical since the isotopic substitution is at the center of mass but, interestingly, the ν₁ stretching frequency for ¹¹BF₃ is found to be 0.198 cm⁻¹higher than for the lighter ¹⁰BF₃ isotopomer. This counterintuitive result is reproduced almost exactly (0.200 cm⁻¹) by ab initio calculations (B3LYP/cc-pVTZ) that included evaluation of cubic and quartic force constants and x_ij anharmonicity constants. The ab initio computations also predict to within 1% the ΔB, ΔC changes in the rotational constants in going from the ground state to the v₁ = 1 vibrational level. The results illustrate nicely the complementary interplay of modern infrared, Raman, and ab initio methods in obtaining and analyzing rovibrational spectra.     

Global fit of the high-resolution infrared spectrum of D2S

High-resolution Fourier-transform spectra of the D₂S molecule in the regions of polyads of interacting vibrational states v = 3/2, 2, 5/2, 3 and 7/2 (v = v₁ + v₂/2 + v₃) were recorded for the first time with a Bruker IFS 120 Fourier-transform interferometer and analysed. A global fit of all currently available rotation-vibration energies has been made for 22 vibrational states of the D₂S molecule. The resulting set of 231 parameters reproduces all the initial experimental data (about 3670 vibration-rotation energies which correspond to more than 9700 ro-vibrational transitions with J^max = 25) with accuracies close to the experimental uncertainties.     

Measurements and theoretical calculations of N2-broadening and N2-shift coefficients in the ν2 band of CH3D

In this paper, we report measured Lorentz N₂-broadening and N₂-induced pressure-shift coefficients of CH₃D in the ν₂ fundamental band using a multispectrum fitting technique. These measurements were made by analyzing 11 laboratory absorption spectra recorded at 0.0056 cm⁻¹ resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 10.2 and 25 cm. The total sample pressures ranged from 0.98 to 402.25 Torr with CH₃D volume mixing ratios of 0.01 in nitrogen. We have been able to determine the N₂ pressure-broadening coefficients of 368 ν₂ transitions with quantum numbers as high as J″ = 20 and K = 16, where K″ = K′ ≡ K (for a parallel band). The measured N₂-broadening coefficients range from 0.0248 to 0.0742 cm⁻¹ atm⁻¹ at 296 K. All the measured pressure-shifts are negative. The reported N₂-induced pressure-shift coefficients vary from about −0.0003 to −0.0094 cm⁻¹ atm⁻¹. We have examined the dependence of the measured broadening and shift parameters on the J″, and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = −J″, J″, and J″ + 1 in the ^QP-, ^QQ-, and ^QR-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.7%. The N₂-broadening and pressure-shift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom-atom Lennard-Jones potential. The theoretical results of the broadening coefficients are in good overall agreement with the experimental data (8.7%). The N₂-pressure shifts whose vibrational contribution is derived from parameters fitted in the ^QQ-branch of self-induced shifts of CH₃D, are also in reasonable agreement with the scattered experimental data (20% in most cases).