The rotational spectrum of 13C2HD in the ground and excited bending states

The pure rotational spectrum of ¹³C₂HD was recorded in the range 100–700 GHz. Lines belonging to the ground vibrational state were observed from J^″ = 1 to J^″ = 11. Several absorption lines were also detected in the bending states v₄ = 1 (Π), v₅ = 1 (Π), v₄ = 2 (Σ⁺ and Δ), v₅ = 2 (Σ⁺ and Δ), v₄ = v₅ = 1 (Σ^?, Σ⁺ and Δ), v₄ = 3 (Π and Φ) and v₅ = 3 (Π and Φ). The transition frequencies measured in this work were fitted together with all the infrared lines available in the literature. The global fit allowed a very accurate determination of the vibrational, rotational and ?-type interaction parameters for the bending states of this molecule.     

Dark resonances for ground-state transfer of molecular quantum gases

One possible way to produce ultra-cold, high-phase-space-density quantum gases of molecules in the rovibronic ground state is given by molecule association from quantum-degenerate atomic gases on a Feshbach resonance and subsequent coherent optical multi-photon transfer into the rovibronic ground state. In ultra-cold samples of Cs₂ molecules, we observe two-photon dark resonances that connect the intermediate rovibrational level |v=73,J=2〉 with the rovibrational ground state |v=0,J=0〉 of the singlet X ¹ Σ _g ⁺ ground-state potential. For precise dark resonance spectroscopy we exploit the fact that it is possible to efficiently populate the level |v=73,J=2〉 by two-photon transfer from the dissociation threshold with the stimulated Raman adiabatic passage (STIRAP) technique. We find that at least one of the two-photon resonances is sufficiently strong to allow future implementation of coherent STIRAP transfer of a molecular quantum gas to the rovibrational ground state |v=0,J=0〉.     

C2H221分子转动角动量定向分布(Orientation)及其碰撞弛豫和转移

利用圆偏振激光受激Raman抽运,以 C₂H₂分子为样品选择性地制备了它的电子基态单一转动态(X¹Σ⁺_g,ν″₂＝1,J″的角动量定向布居(orientation)．并从圆偏振紫外激光诱导的A¹A_u(ν′₃＝1)←X¹Σ⁺_g(ν″₂＝1)的荧光（谱）,直接测定了 C₂H₂(X¹Σ^＋_g,ν″₂＝1,J″＝4,7,8,…,13）的角动量定向布居值．从时间分辨的荧光信号谱测定了角动量定向布居的碰撞弛豫速率常数,同时还研究了由各初始激励的转动态向其他邻近转动态碰撞诱导的角动量定向布居转移． 关键词：     

The stretching fundamental bands of 13C2D2

The stretching fundamental bands of the isotopically substituted acetylene ¹³C₂D₂ have been recorded and analysed. The Raman spectra of the Q branch of v ₁ and v ₂, Σ⁺ _g -Σ⁺ _g bands, have been recorded with an instrumental resolution of about 3.0 x 10^?3 cm^?1 using inverse Raman spectroscopy. The infrared spectrum has been recorded in the region between 2350 cm^?1 and 2500 cm^?1 with an instrumental resolution of 4.0 x 10^?3 cm^?1. Transitions belonging to the v ₃, Σ⁺ _u -Σ⁺ _g , fundamental band have been identified and assigned. The vibrational energies and the rotational and centrifugal distortion constants of the excited states of all the observed transitions have been determined. The molecular parameters obtained reproduce the assigned wave-numbers with a standard deviation of the same order of magnitude as the experimental uncertainty.     

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.     

Effect of polarization on population transfer in H2 by stimulated Raman transition with partially overlapping laser pulses

Polarization effects on population transfer by stimulated Raman transition using overlapping time dependent pump and Stokes laser pulses from the ground X ¹Σ _g ^/+ (v _g=0, J _g=1) level of H₂ to the final X ¹Σ _g ^/+ (v _f=1, J _f=1) level via the intermediate B ¹Σ _u ^/+ (v _i=14, J _i=0,2), C ¹Π _u ^/+ (v _i=3, J _i=2) and C ¹Π _u ^/− (v _i=3, J _i=1) levels have been theoretically investigated by applying the density matrix formalism. We have studied in detail the dependence of the population transfer on time delay between two pulses for the cases of on-resonance excitations considering linear parallel and same-sense circular polarizations of the fields. The pump and Stokes fields are taken as having Gaussian pulse shapes with peak intensities I _P ^/0 (I _S ^/0 )=2 × 10⁶ and 1 × 10⁷ W/cm². Density matrix equations have been solved for each value of the magnetic quantum number M _g(0, ±1) of the initial ground level taking into account the M _g dependence of the Rabi frequencies. M _g — averaged population transfer to the final level has also been calculated. For resonance excitations to the B(14, 0) or C(3, 1) levels, appreciable population transfer is achieved for intuitive pulse order for some particular values of M _g and M _i (magnetic quantum number of the resonant intermediate level) depending on the nature of polarizations. The calculated values of M _g — averaged population transfer for the two cases of polarizations show that for on-resonance excitation to the B(14, 0) or the C(3, 1) level, linear parallel polarization of the laser fields yield more transfer efficiency whereas for resonance excitation to the B(14, 2) level, larger population transfer results from the same-sense circular polarizations. For resonance excitation to the C(3, 2) level, M _g — averaged population is found to be almost polarization independent. The calculations for the six-level H₂ system reveal some interesting features of polarization effects on the population transfer efficiency.     

Concentration effects on absolute depolarized Rayleigh ratios and effective polarizability derivatives of CS2 in liquid mixtures with CCl4

Experimental results are reported from polarized and depolarized Raman intensity measurements in combination with absolute depolarized Rayleigh ratios of liquid CS₂ in CCl₄ mixtures at 25°C. Using a calibrated Raman spectrometer it was possible to determine the concentration dependence of g ₂ · γ² _eff of CS₂. Intensity measurements of the polarized and depolarized Raman spectra of the symmetric stretching vibration of CS₂ under the same conditions allowed the determination of the effective values of α₀₁ and γ₀₁ respectively to the normal mode Σ⁺ _g in the liquid phase. In the neat liquid, α₀₁ = 0·19 ų and γ₀₁ = 0·22 ų. In mixtures with CCl₄ the values of α₀₁ decrease at lower CS₂ concentration whereas the values of γ₀₁ increase. These results indicate that the isotropic induced dipole field is increasingly cancelled as the environment becomes more isotropic while the anisotropic part is amplified in CCl₄. A report is also given of an anomalous concentration behaviour of the intensity of the combination mode v ₁ + v ₂-v ₂ on the low frequency side of the v ₁ transition which is amplified relative to the intensity of the v ₁ mode as the CCl₄ concentration increases.     

Efficiently generated rotational and vibrational stimulated raman emission by means of a two-color laser beam

When a two-color laser beam is introduced into pressurized hydrogen, about 40 laser emission lines are generated from the ultraviolet to the visible regions. This phenomenon is ascribed to the stimulated Raman effect due to a combination ofJ=1 J=3 rotational andv=0 v=1 vibrational transitions. By introducing the two-color laser beam, the threshold for generation of the rotational line is substantially reduced. The present phenomenon is attributed to four-wave mixing, which allows efficient generation of higher-order rotational and vibrational Raman lines.     

Optical Stark effects in the stimulated Raman spectrum of molecular oxygen

High-resolution stimulated Raman spectroscopy has been used to observe optical Stark effects in pure-spin, rotational, and rotational-vibrational transitions in molecular oxygen (X³Σ_g^?). Recorded spectra in both polarized and depolarized configurations demonstrate some striking differences in the Stark splitting of ³Σ ground state molecules from that reported previously for ¹Σ molecules. An analysis of the position of a number of normal and satellite rotational-vibrational lines in both the polarized and depolarized spectra has led to a measurement of a value for the v = 1 excited state polarizability anisotropy and to a more accurate value for the band origin of the v = 1 ← 0 transition: γ₁ = (α_| ? α_|)₁ = (1.36 ± 0.17) × 10^?24 cm³, and ν₀ = 1556.385 ± 0.001 cm^?1.     

Transfer of rotational population in CO by IR laser double resonance

A double resonance experiment on CO using two CO lasers (pump on v = 1 → 0, probe on v = 2 → 1) is described. Molecular diffusion has to be considered to reduce the data. The total rotational relaxation rate constant for J = 10 is found to be 1.25 ± 0.15 s^-1 torr^-1. Population transfer seems to proceed for $\text{2}\text{3}$ by |ΔJ| = 1 and for $\text{1}\text{3}\text{by |ΔJ| =2}$.     

A novel demonstration of photoacoustic Raman spectroscopy with combined stimulated Raman pumping in H2 molecule

We present the experimental demonstration of a novel, efficient, and vibrational selective technique to prepare population in vibrational level v″ = 1 using the stimulated Raman pumping. Photoacoustic Raman signal has been studied in non-radiative transitions in the molecule H₂ (v″ = 0) and (v″ = 1). The population fraction in the v″ = 1 level can be estimated by using combined photoacoustic Raman spectroscopy with stimulated Raman pumping for the first time.     

Franck-Condon Factors and r-Centroids for the (B [sbnd] X) and (C [sbnd] X) Bands of the 107Ag 109Ag Molecule

Arrays of Franck-Condon factors q(v′, v″) and r-centroids r(v′, v″) were computed using Morse potentials for C¹Π [sbnd] X¹Σ⁺ _g and B O⁺ _u [sbnd] X¹Σ⁺ _g bands of the ¹⁰⁷Ag ¹⁰⁹Ag molecule.     

The rotational levels of the ground vibrational state of formaldehyde

A variational procedure for rovibrational energy levels and wavefunctions of centrally connected tetra-atomic molecules is extended to include high rotational states, and in particular, J ? 10 levels for the vibrational ground state of formaldehyde. It is very important to do this because it has made possible the calculation of the usual rotational spectroscopic constants which correspond to the forcefield and geometry. A direct comparison with the ‘observed’ spectroscopic constants is therefore possible. The geometry and forcefield are refined against 65 J = 0 levels of H₂CO, 6 J = 0 levels of D₂CO, 42 J = 1, 70 J = 2 and 98 J = 3 levels of the ground and fundamentals of H₂CO and D₂CO, using an iterative scheme. The mean absolute error of the J = 0 levels is 1·10 cm^?1 and that for J ≠ 0 is 0·005 cm^?1, and the predicted geometry is CH = 1·10064 Å, CO = 1·20296 Å and HCO = 121·648°. Finally, the rotational constants A, B, and C for the ground state are 281956, 38846 and 34003 MHz, compared with the observed values 281971, 38836, and 34002 MHz. The centrifugal distortion constants Δ_J , Δ_JK , Δ_K and δ_J , are 77, 1275, 18113 and 11 kHz compared with 75, 1291, 19422 and 10 kHz. These results underline the accuracy of the new quartic forcefield.     

Determination of the helium-4 mass in a Penning trap

The determination of the rotational quadrupole alignment of diatomic molecules via REMPI detection is investigated. In this process a high focal intensity usually increases the detection probability. At high intensities the AC Stark effect may cause a splitting of the normally degenerate m_J sublevels of a rotational state J beyond the spectral width of the exciting radiation. This leads to a selective detection of only certain m_J states with the consequence that deduced alignment factors can be misleading. From the theoretical considerations line profiles are explicitly calculated for dynamic polarizabilities which represent the B ¹Σ⁺ _u←X ¹Σ⁺ _g transition of H₂, in order to fit an experimental (3+1) REMPI spectrum and to predict (1+1') line shapes as a function of laser intensity. It is further shown that the deduced quadrupole alignment factor A ₀ ⁽²⁾ is significantly changed by the second order AC Stark effect when the intensities are chosen high enough to observe asymmetric broadened line profiles. Different combinations of relative linear polarizations of the exciting and ionizing laser beams are discussed. Received 1st August 2000 and Received in final form 2 May 2001     

The absorption spectrum of 12C2H2 between 12800 and 18500cm−1 II. Rotational analysis

The rotational structure of the vibrational bands of ¹²C₂H₂ is investigated in three spectral energy regions not previously systematically explored at high resolution, 12800–13500 cm^?1, 14000–15200 cm^?1 and 16500–18360 cm^?1, on the basis of new spectral data recorded by intracavity laser absorption spectroscopy. The rotational analysis of 17 new absorption bands arising from the ground state is reported (11 Σ_u ⁺ ? Σ_g ⁺ bands and 6Π_u ? Σ_g ⁺ bands). Four bands in the range studied show strong perturbations affecting both the line positions and intensities. Their detailed analysis is performed in order to determine the nature of the coupling schemes, the vibrational species and the rotational constants of the perturber states. Altogether, the vibration-rotation parameters of 21 newly observed vibrational states are derived.     

New observations and analyses of the laser excited fluorescence of the A1Σu+-X1Σg+ bands of the Na2 molecule

A medium power (～50 mW, 6328 Å) HeNe laser is used to excite the A¹Σ_u⁺-X¹Σ_g⁺ fluorescence of the Na₂ molecule in a crossed heat pipe oven. The spectrum in the region 5800–8500 Å is recorded both photographically (3.4 M Ebert) and photoelectrically (GaAs detector) with an emphasis on accurate relative intensities and on the observation of higher vibrational levels in the ground state close to the dissociation limit. P and R doublets in four series originating from (v′ = 14, J′ = 45), (v′ = 16, J′ = 17), (v′ = 22, J′ = 86), and (v′ = 25, J′ = 87) levels are observed and identified. The first two series, known from earlier work, are extended further to longer wavelengths to include 13 to 17 additional ground-state vibrational levels. The latter two series are observed for the first time. They originate from higher J′ levels and span a wide range of v″ levels (0 ≤ v″ ≤ 48). Effective RKR potentials for specific J″ (= 17, 45, 86, and 87) quantum numbers of the ground state are constructed and from them the true (rotationless) potential energy curve (for X¹Σ_g⁺) is derived which (a) reproduces the RKR curve previously given by Kusch and Hessel and (b) extends the curve from 5.77 to 7.26 Å (outer turning point). The dissociation energy D_e is estimated from these data to be 6022 ± 21 cm^?1.     

Raman study of CF4 in liquid Ar

The rotational behaviour of CF₄ dissolved in liquid argon is derived from the band contour analysis of Raman spectra recorded over the concentration range from 10^-2 mole fraction to 1 mole fraction at 85 K. The angular momentum correlation times have been determined with the help of the J-diffusion model and used to apply the rough hard sphere model. A study of the transition dipole-transition dipole (TD-TD) interaction is made using the v ₃ mode at 85 K for different concentrations.     

Raman紫外双共振研究C2H2分子的碰撞转动弛豫

本文利用受激Raman抽运,选择性地制备了C₂H₂分子电子基态的红外非激活振动能级的单一转动态(X¹∑_g⁺,v″₂=1,J″=9,11,13),并从紫外激光诱导的A¹Au(v′₃=1)←X¹∑_g⁺(v″₂=1)荧光谱,直接测定上述三个转动态的C< 关键词：     

Variational calculations on the hydrogen molecular ion

We present high-precision non-relativistic variational calculations of bound vibrational—rotational state energies for the H⁺ ₂ and D⁺ ₂ molecular ions in each of the lowest electronic states of Σ _g , Σ _u , and Π _u symmetry. The calculations are carried out including coupling between Σ and Π states but without using the Born—Oppenheimer or any adiabatic approximation. Convergence studies are presented which indicate that the resulting energies for low-lying levels are accurate to about 10^?13. Our procedure accounts naturally for the lambda-doubling of the Π _u state.