Infrared spectrum of the Ar-CO complex: observation of the v co = 2 ← 0 band at 4260 cm −1

The spectrum of the weakly-bound van der Waals complex Ar-CO has been observed for the first time in the region of the CO vibrational overtone, using a long-path (180 m) low-temperature (64 K) absorption cell and a Fourier transform infrared spectrometer. The appearance of the spectrum was very similar to that studied previously in the v _co = 1 ← 0 region. However, it was very much weaker, so a detailed analysis was only possible for the relatively uncongested K = 1 ← 0 and 0 ← 1 subbands. The parameters determined here for these sub-bands should help to constrain the C-O bond length dependence of the Ar-CO intermolecular potential in future theoretical models.     

Isotope dependent predissociation in the C 1 Σ + , v =0 and v =1 states of CO

Rotationally resolved spectral lines in the C - X (1, 0) band of carbon monoxide are investigated under high resolution using a coherent vacuum ultraviolet laser source, continuously tunable near 107 nm. Transition frequencies are determined by calibrating against a reference standard of iodine lines, recorded with saturation spectroscopy in the visible range, yielding an absolute accuracy of 0.003 cm^-1 in the vacuum ultraviolet. Improved molecular constants for the excited state are derived and no effects of perturbation are found at the present level of accuracy. Line broadening measurements result in information on the excited state lifetime of the C ¹ Σ ⁺ , v = 1 state for five natural isotopomers of carbon monoxide: τ( ¹² C ¹⁷ O ) = 280 ps, τ( ¹² C ¹⁸ O ) = 210 ps, τ( ¹³ C ¹⁶ O ) = 295 ps, τ( ¹³ C ¹⁷ O ) = 160 ps, and τ( ¹³ C ¹⁸ O ) = 150 ps. Within the accuracy of the present measurements no effects of J-dependent lifetimes were observed, for neither of the isotopomers. In addition direct time domain measurements of the lifetime of the C ¹ Σ ⁺ , v = 0 and v = 1 states of the main isotopomer are performed in a pump-probe experiment using a picosecond VUV-laser, yielding τ( ¹² C ¹⁶ O ) = 1780 ps for v = 0 and τ( ¹² C ¹⁶ O ) = 625 ps for v = 1. For C ¹ Σ ⁺ , v = 0 in ¹²C¹⁶O and ¹³C¹⁶O the same lifetime is found; this lifetime matches experimental values of the oscillator strength and hence supports previous results showing pure radiative decay in this state; the error margins however do not exclude some low level of predissociation. The measurements indicate that the C ¹ Σ ⁺ , v = 0 state of the ¹³C¹⁸O isotopomer is predissociated with an estimated yield of 17% (i.e. above the level of predissociation for ¹²C¹⁶O.) From the combined data predissociation yields upon excitation of the C ¹ Σ ⁺ , v = 1 state are derived, lying in the range 0.84-0.91 for the five less abundant isotopomers; for the main ¹²C¹⁶O isotopomer a strongly deviating predissociation yield of 0.65 is deduced. Received 21 December 2000 and Received in final form 26 March 2001     

Observation of the v′=8←v=0 vibrational overtone in cold trapped HD+

We report the observation of the hitherto undetected v′=8←v=0 vibrational overtone in trapped HD⁺ molecular ions, sympathetically cooled by laser-cooled Be⁺ ions. The overtone is excited using 782 nm laser radiation, after which HD⁺ ions in v=8 are photodissociated by the 313 nm laser used for Be⁺ cooling. The concomitant loss of HD⁺ is detected by the method of secular excitation (Roth et al. in Phys. Rev. A. 74:040501(R), 2006). We furthermore present details of the experimental setup, and we show that results from spectroscopy of v′=8←v=0 overtones in combination with accurate ab initio calculations may yield a new value for the proton–electron mass ratio with an accuracy of order 1 ppb.     

Rotational analysis of the v 2 + v 6 ±1, v 5 ∓1 + v 6 ∓1 and v 5 ∓1 + v 6 ±1 interacting infrared bands of methyl bromide

The rotational analysis of the infrared absorption spectrum of CH₃ ⁷⁹Br and CH₃ ⁸¹Br between 2150 and 2510 cm^-1 was performed on a Fourier transform spectrum with a resolution of 0·007 cm^-1. The bands v ₂ + v ₆(E) and v ₅ + v ₆(A ₁ + A ₂ + E) occur in this region, giving rise to several perturbations as in the corresponding system of methyl chloride [3]. Forbidden transitions, observed in correspondence of the level crossing of the x-y Coriolis coupling between v ₂ + v ₆ and v ₅ + v ₆(E), enabled us to estimate the value of A″ - 225D″_K at 5·16186 cm^-1 for CH₃ ⁷⁹Br and 5·16173 cm^-1 for CH₃ ⁸¹Br. The parallel system of v ₅ + v ₆ exhibits a perpendicular structure, and an l-type resonance couples those levels of the parallel and perpendicular components of v ₅ + v ₆ involved in transitions from the K″ = 0 levels of the ground state. The ^QQ ₀ branches of the A ₂ component of v ₅ + v ₆, made active by this resonance, are observed for both isotopic species.     

The S21 lines of the A2Σ+ (v′ = 1)←X2Π (v″ = 0) transitions of OH and OD

The S₂₁ lines of the OH radical for the A²Σ⁺ (v′ = 1)←X²Π (v″ = 0) transition have been observed in the 278–280 nm region from the laser-excitation spectrum. The OH radical was generated from either the H + NO₂ or the H + O₃ reaction in a flow system and the fluorescence passing through a 309.6 nm interference filter was detected with a photomultiplier-boxcar integrator arrangement. The weak S₂₁ lines were observed at laser energies above 0.2 mJ. The observed peak wavenumbers are in excellent agreement with those predicted for the S₂₁ bands of the A (v>′ = 1)←X (v″ = 0) transition from the known spectroscopic parameters. Observation of the corresponding S₂₁ system for OD in the 286.0–286.9 nm region further confirms this assignment. The relative absorption cross-sections of about one-tenth those of the P₁ lines are in good agreement with theoretical considerations.     

High resolution FTIR spectra of AsD3 in the 20-1000 cm−1 region. The ground, 98, v2 = 1 and v4 = 1 states

The pure rotational spectrum of the near-spherical oblate symmetric top AsD₃ has been recorded in the 20–120cm^?′ region with a resolution of 2.3 × 10^?3 m^?1 employing an FT interferometer. Rotational transitions with 5 ? J ? 29 and 0 ? X ? 25 of the ground state (GS) and the v₂ = 1 and v₄ = 1 excited states have been assigned. Splittings were observed for the GS, 98, K = 3 and 6 levels, the K = 3 levels of v₂ and the kl = ?2, 1, 4 and 7 levels of v₄. Furthermore the x,y Coriolis coupled v₂ and v₄ bands, v ⁰ ₂ = 654.4149cm^?1, and v ⁰ ₄ = 714.3399 cm^?1, have been examined with a resolution of 2.4 × 10^?3 cm^?1, and ca. 2500 allowed and 336 ‘forbidden’ lines with J′_max = 31 and K′_max = 28 have been assigned. Appropriately weighted GS data comprising FIR lines, allowed and ‘forbidden’ (up to ΔK = ±6) GS combination differences, mmw data, and ΔJ = 0, ΔK = ±1 distortion moment transitions were fitted together, and GS parameters complete through H parameters have been determined. Two different reductions of the Hamiltonian, either with ΔK = ±6 (h₃) or ΔK = ±3 (ε) off-diagonal elements, have been employed. Equivalence of these reductions up to J = 22 was established while for J > 22 the ε reduction is superior. The v₂ and v₄ data have been fitted with two equivalent models based on different reductions of the rovibrational Hamiltonian. In addition to the dominating x,y Coriolis resonance, ζ ^y ₂₄ 0.520, Δ(k ? l) = ±3 and ±6 interactions are important and were accounted for by the models. The transition moment ratio |M₄: M₂| =0.75 has been determined, with a positive sign of the product M ₂ζ ^y ₂₄ M ₄. An improved r₀ structure, r₀(AsD) = 1.51753 Å and α₀(DAsD) = 92.000°, has been determined.     

First-principles investigation of the phonon spectrum of β-GaS

This paper presents the results of the first-principles density functional theory calculation of the phonon spectrum of the ??-GaS semiconductor with a layered structure. The elastic constants and velocities of sound along and across the layers of the ??-GaS semiconductor have been determined. Investigation of the equilibrium structure and the phonon spectrum of the (0001) surface of the ??-GaS crystals has demonstrated that the bulk and surface structural and dynamical properties of these crystals differ only slightly. The calculated frequencies and symmetries of phonon modes at the center of the Brillouin zone of the semiconductor are in satisfactory agreement with the experimental data obtained from the Raman and infrared spectra.     

Analysis of the low—lying spectrum of the He—tetramer

There is a type of nodal surface imposed by symmetry on wavefunctions.These surfaces are crucial to the ordering of low-lying states.Based on an analysis of this type of surface and based on existing theoretical results,the feature of the low-lying spectrum of the He-tetramer is studied,and the candidates of bound states and narrow resonances are suggested.     

A comprehensive model to predict the microwave spectrum of propyne in the region 17–70 GHz for the ground and v10 = 1, 2, 3, 4, 5 vibrational states

A comprehensive model for predicting rotational frequency components in various v₁₀ vibrational levels of propyne was developed. A number of components of the rotational spectra in the ground and v₁₀ = 1, 2, 3, 4 excited vibrational states of propyne in the frequency range 17–70 GHz have been obtained. Molecular constants for these vibrationally excited states have been determined from more than 100 observed rotational transitions. From these experimentally observed components and a model based upon first principals for C_3v molecules, rotational constants have been expressed in a form which enables one to predict rotational components for vibrational levels for propyne up to v₁₀ = 5. The model also appears to be useful in predicting rotational components in more highly excited vibrational levels but data were not available for comparison with the theory. Experimentally measured frequencies are presented and compared with those calculated using the results of basic perturbation theory.     

The stereodynamic properties of the F + HO (v,j)→HF + O reaction on the 1A' and 3A' potential energy surfaces by quasi-classical trajectory: Initial excitation effect (v =1-3, j = 0 and v = 0, j =1-3)

The stereodynamic properties of the F + HO (v, j) reaction are explored by quasi-classical trajectory (QCT) calculations performed on the ¹A' and ³A' potential energy surfaces (PESs). Based on the polarization-dependent differential cross sections (PDDCSs) and the angular distributions of the product angular momentum with the reactant at different values of initial v or j, the results show that the product scattering and product polarization have strong links with initial vibrational-rotational numbers of v and j. The significant manifestation of the normal DCSs is that the forward scattering gradually becomes predominant with the initial vibrational excitation increasing, and the scattering angle of the HF product taking place on the ³A' potential energy surface is found to be more sensitive to the initial value of v. The product orientation and alignment are strongly dependent on the initial rovibrational excitation effect. With enhancement in the initial rovibrational excitation effect, there is an overall decrease in the product orientation as well as in the product alignment either perpendicular to the reagent relative velocity vector k or along the direction of the y axis, for which the initial rotational excitation effect is much more noticeable than the vibrational excitation effect. Moreover, the initial rovibrational excitation effect on the product polarization is more pronounced for the ³A' potential energy surface than for the ¹A' potential energy surface.     

Analysis of the EPR spectrum of γ-irradiated barium dithionate

An analysis of the experimental EPR spectrum of -irradiated barium dithionate is made. Based on the data obtained, a model of this spectrum is constructed. It is shown that the spectrum results from superposition of four individual signals, for which the following values of the g-factor components have been determined: for I g = 2.0097, g = 2.0044; for II g = 2.0069, g = 2.0023; for III g = 2.0042, g = 2.0032; for IV g = 2.0002 and g = 2.0032.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 727–731, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Relative probabilities of spontaneous transitions in v″ progressions of the G1Σ g + , v′→B 1Σ u + , v″ bands of the H2 molecule

The probabilities of spontaneous transitions in v″ progressions of the G ¹Σ _g ⁺ →B ¹Σ _u ⁺ bands of the H₂ molecule (the 3D→2B electronic transition in notations of G.H. Dieke) are, for the first time, experimentally studied. The line strength ratios were measured for 78 G ¹Σ _g ⁺ , v′, J′→B ¹Σ _u ⁺ , v″, J″ electronic-vibrational-rotational spectral lines having a common upper level but belonging to different bands of v″ progressions (the vibrational branching coefficients). For this purpose, the intensities of lines of the P and R branches, emitted by a low-pressure plasma and corresponding to different values of the rotational (J′=0–11) and vibrational (v′=0–3 and v″=0–7) quantum numbers, were used. It was found that the changes in the vibrational branching coefficients with variation of v′ and v″ are significant (up to a factor of 20). For most bands studied, the dependences of the vibrational branching coefficients on the rotational quantum number J′ of an upper level are rather weak and do not exceed 30%. It was established that the difference between the experimental values of ratios of the vibronic transition probabilities (summed over J″) and the results of calculation in the adiabatic approximation strongly depends on v′, reaching a factor of 25 for a transition from the v′=2 level. At the same time, the discrepancy between the experimental data and the results of nonadiabatic ab initio calculations lies between 1.0 and 2.3.     

Neutrino mass spectrum with vμ → vs oscillations of atmospheric neutrinos

We consider the “standard” spectrum of the active neutrinos (characterized by strong mass hierarchy and small mixing) with additional sterile neutrino, v_s. The sterile neutrino mixes strongly with the muon neutrino, so that v_μ ↔ v_s oscillations solve the atmospheric neutrino problem. We show that the parametric enhancement of the v_μ ↔ v_s oscillations occurs for the high energy atmospheric neutrinos which cross the core of the Earth. This can be relevant for the anomaly observed by the MACRO experiment. Solar neutrinos are converted both to v_μand v_s. The heaviest neutrino (≈ v_τ) may compose the hot dark matter of the Universe. The phenomenology of this scenario is elaborated and crucial experimental signatures are identified. We also discuss properties of the underlying neutrino mass matrix. 1998 Published by Elsevier Science B.V.     

Recent progress with the CO-overtone Δv=2 laser

We report the recent progress in the performance of the CO-overtone v=2 laser. We were able to increase both the number of lines and the output power by a significant amount. This laser is now a reliable source for spectroscopic applications in the spectral region from 2500–3800 cm^–1. The typical parameters of the laser plasma and a table with the observed laser transitions and their frequencies are given.     

The high-resolution spectrum of the ν1 (A1) band of 12CD3F

The spectrum of the ν₁ (A₁) band of ¹²CD₃F has been recorded with a resolution of 0.010 cm⁻¹ and deconvolved to 0.005 cm⁻¹. Over 1050 transitions have been assigned with K ≤ 16 and J ≤ 42. The spectrum is highly perturbed, exhibiting avoided crossings in most of the observed sub-bands. The origin of most of the local and global resonances has been determined and the coupling constants estimated. Due to the complexity of the spectrum resulting from the 24 potential interacting states in the region, the assigned frequencies were fitted in a restricted manner (K ≤ 3, J ≤ 15), to obtain the following effective constants for the band: ν₀ = 2090.8118(20) cm⁻¹, α^A = 1.19743 × 10⁻² cm⁻¹, and α^B = −1.8489 × 10⁻³ cm⁻¹. From an unrestricted least-squares analysis, fixing the above parameters the β's (D_v^x = D₀^x − β_v^x) were calculated to be β^J = 1.7776 × 10⁻⁷ cm⁻¹, β^JK = 8.3406 × 10⁻⁷ cm⁻¹, and β^K = −6.3829 × 10⁻⁷ cm⁻¹. These constants serve as good starting parameters for the global analysis necessary to fully analyze the 5-μm region of the ¹²CD₃F spectrum.