High-Resolution Laser Spectroscopy of YbCl: The AΠ–XΣ Transition

The A²Π–X²Σ⁺ transition of ¹⁷⁴Yb³⁵Cl and ¹⁷²Yb³⁵Cl has been rotationally analyzed for the first time. Doppler-limited laser excitation spectroscopy with selective detection of fluorescence was used to obtain spectra of the 0–0 and 1–0 bands with a measurement accuracy of approximately 0.0035 cm⁻¹. Resolved fluorescence was used to record the 0–1, 0–2, and 0–3 bands and to unequivocally assign the rotational numbering, N, to the laser excitation spectra. In total, over 1300 line positions have been measured and assigned for each of the two isotopomers and employed in least-squares fits of molecular parameters. The principal results for the A²Π state are A_e = 1491.494(2) cm⁻¹ and R_e = 2.4433(1) Å, and for the X²Σ⁺ state, R_e = 2.4883(2) Å and γ_e = 4.59(2) × 10⁻³ cm⁻¹. The interaction between the X²Σ⁺ and A²Π states has been investigated and is shown to be the main contributor to the spin–rotation splitting in the ground state.     

Spectroscopic Study of the Na2 2Σg State by cw Perturbation-Facilitated Optical-Optical Double-Resonance Spectroscopy

The Na₂(3sσ_g)(4sσ_g) 2³Σ⁺_g state of Na₂ has been observed and studied by cw perturbation-facilitated optical-optical double-resonance (PFOODR) spectroscopy for the first time. A single-mode dye laser and a Ti-sapphire laser served as the pump and the probe lasers, respectively. A total of 543 PFOODR excitation signals have been assigned to the 2³Σ⁺_g ← b³Π_1u transitions. Absolute vibrational numbering was determined by counting nodes in the 2³Σ⁺_g → a³Σ⁺_u bound-free spectra. Spectroscopic constants and the corresponding RKR potential energy curve are presented in this vsork. The values of T_e, R_e, and D_e, are found to be 25 551.237(49) cm⁻¹, 3.53463(35) Å, and 6211.5(1) cm⁻¹ respectively.     

Isotope and Hyperfine Structure in the "Orange" System of FeO: Evidence for Two Δi Excited States

The orange system of FeO has been reinvestigated using low-temperature molecular beam laser-induced fluorescence spectra, obtained by supersonic jet cooling. Two new weak bands have been found, and analyses of some of the previously known bands extended. Measurements of the ⁵⁴Fe-⁵⁶Fe isotope shifts have been made for most of the bands, and the hyperfine structure of the low-J lines has been recorded for two of the strongest bands of ⁵⁷FeO. The isotope shifts are consistent with the presence of two ⁵Δ_i-⁵Δ_i transitions lying within 1000 cm⁻¹; the origins of the Ω = 4 spin components lie at 5583 and 6110 Å, respectively. The hyperfine patterns and the spin-orbit structure indicate that the upper state electron configurations are (3dδ)³ (3dπ)² (3dσ)¹, (D⁵Δ_i, 5583 Å) and O(2pπ)³ (4sσ)¹ (3dδ)³(3dπ)³, (D′⁵Δ_i, 6110 Å). The bond length in the D′ state (r₀ = 1.654 Å) has been obtained from a deperturbation of the 6110 Å band; it is only 0.035 Å longer than in the ground state, which indicates that electron promotion between the two π orbitals, nominally O(2pπ) and Fe(3dπ), has only a small effect on the strength of the bonding. The new isotope data still do not clarify the vibrational assignments of the higher levels, which are disorganized by extensive electronic perturbations.     

The electronic spectrum of bismuth monofluoride: A reinvestigation of the A0-X10 system

A reinvestigation of the A0⁺-X₁0⁺ band system, the most electronic transitions reported for bismuth monofluoride, is presented. Approximately 65 bands were photographed in emission between 4220 and 5417 Å, of which 33 were rotationally analyzed. Inconsistencies in earlier vibrational analyses were resolved. Rotational constants for 0 ≤ ν′ ≤ 12 and 0 ≤ ν″ ≤ 18 were determined from direct least-squares fitting to the measured line positions of each band. “Merging” of the overdetermined constants was performed to obtain the best single estimate of each parameter. The resulting minimum-variance linear unbiased estimates were used to calculate RKR potential curves. Franck-Condon factors and r centroids were subsequently obtained and are presented. Evidence is given for predissociation in the upper state; perturbations involving levels above the crossing point are correlated with those previously reported in the B0⁺ state. The upper limit of the ground-state dissociation energy (3.14 eV) is in accord with extrapolated values as given in earlier investigations. The nature of a postulated third interacting state is also discussed.     

Argon ion laser-induced BaS BΣ-AΣ, A′Π, aΠ, and XΣ fluorescence spectra: Analysis of A A′, A a, and A′ a perturbations

The 333.6-, 351.1-, and 363.8-nm lines of a cw argon ion laser are found to coincide with the BaS B¹Σ⁺-X¹Σ⁺ (12, 0) R(17), (6, 0) P(35), and (3, 0) R(125) transitions, respectively. Fluorescence transitions from the laser-prepared upper levels terminating in X¹Σ⁺ V = 0–28, A¹Σ⁺ V = 1–3, A′¹Π V = 1–13, and a³Π₁ V = 3–12 are assigned. These results are combined with a previous analysis of the extensively perturbed BaS A¹Σ⁺-X¹Σ⁺ system [R. F. Barrow, W. G. Burton, and P. A. Jones, Trans. Farad. Soc.67, 902–906 (1971)]. Every observed perturbation of the BaS A¹Σ⁺ state is electronically and vibrationally assigned. The levels a³Π₀ V = 10–13, a³Π₁ V = 12–14, a³Π₂ V = 15, and A′¹Π V = 10–13 are sampled via their perturbations of A¹Σ⁺ V = 0–2. Although the mutual interactions of the a³Π, A′¹Π, and A¹Σ⁺ states approach Hund's case (c) limit, a complete deperturbation is performed from a case (a) starting point. Of the five lowest energy electronic states of BaS, only b³Σ⁺ remains uncharacterized. Principal deperturbed molecular constants are (in cm⁻¹, 1σ uncertainties in parentheses):

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The E(4) Πu state in K2 and its perturbations

The E(4) ¹Π_u←X ¹Σ⁺_g band system of the K₂ molecule is investigated by the technique of Doppler-free optical–optical double resonance polarization spectroscopy. The observed vibrational levels v=0 to 9 of the E state are subject to numerous rotational perturbations by the neighboring 4 ³Π_u, 4 ¹Σ⁺_u, and 5 ³Σ⁺_u electronic states. By using deperturbation methods, the potential curves of the 4 ¹Π_u and 4 ³Π_u states are determined as well as some properties of the 4 ¹Σ⁺_u and 5 ³Σ⁺_u state potentials. The results are compared with predictions of ab initio calculations.     

Laser Spectroscopy of the CCO Radical in the 0.77-μm Region: Analysis of theÃ(020)κΠ andÃΠi(001) States

TheÃ(020)κ³Π–X³Σ⁻(000) andóΠ_i(001)–X³Σ⁻(000) bands of the CCO radical have been investigated by laser spectroscopy with two types of tunable laser system. An analysis was made simultaneously for both the bands to establish line assignments and determine molecular constants for both theÃ(020) andÃ(001) states. A coupling constant between these two states was also determined by assuming the interaction to be of Fermi type.     

The π ← n transition of formic acid

New sharp bands of formic acid have been observed in the near ultraviolet at the long wave-length end of the previously observed diffuse band system (2250–2500 Å) by considerably extending the absorption path length. Both the diffuse and sharp bands belong to the same vibrational system which is assigned to the π^* ← n electronic transition in the carbonyl group. Extensive progressions are observed in the carbonyl stretching frequency which is greatly reduced in the excited state (fundamental ν₃′ ≈ 1080 cm⁻¹) and many intervals of about 400 cm⁻¹ are assigned to the OCO bending frequency ν₇′.A band contour analysis of the 2593 Å band shows that the molecule is nonplanar in the excited state because of the magnitude and sign of the inertial defect. From this analysis, the rotational constants for the excited state are S^‘=1.8755, B^‘0.4042, C^‘=0.3378cm⁻¹ By the plausible assumption that the important changes in the molecule are in the C=0 bond length, the OCO angle, and the nonplanarity due to the formyl hydrogen, the following excited state parameters are derived.rC=0 = 1.407A.The changes in formic acid are closely analogous to the changes in formyl fluoride as a result of the π^* ← n transition.     

Rotationally Resolved Vacuum Ultraviolet Laser Spectra of theCl21Σu←XΣgTransition

Rotationally and isotopically resolved single-photon excitation spectra of jet-cooled Cl₂in the wavelength region between 133 and 138 nm were recorded using a tunable vacuum ultraviolet “laser” generated by two-photon resonantly enhanced four-wave difference mixing in Kr gas. The dominant transition (1¹Σ⁺_u←X¹Σ⁺_g) is well known theoretically and experimentally to involve a double-well excited state potential energy curve formed by a strong homogeneous Rydberg-state/ion-pair state avoided crossing. In this work, single isotopomer spectra were obtained by dispersing and detecting ions produced by (1 + 1′) resonance-enhanced multiphoton ionization in a time-of-flight mass spectrometer. In this way, rotational constants were deduced for the first time for many v′ levels of the least abundant molecular isotope,³⁷Cl₂, which are both localized in the Rydberg well, and delocalized in the ion-pair portion of the 1-state potential energy curve. Our experimentally derived band origins andB^′_vvalues test the practical validity of an analytical 1¹Σ⁺_upotential energy function which is a modified version of the one first proposed by J. Wörmer, T. Möller, J. Stapelfeldt, G. Zimmerer, D. Haaks, S. Kampf, J. Le Calvé, and M. C. Castex (1988. Z. Phys. D,7,383–395).     

High-Resolution Study of the BaI AΠ Electronic State

Near-infrared and visible spectra of the A²Π–X²Σ⁺, C²Π_1/2–A²Π_1/2, C²Π_1/2–B²Σ⁺, and C²Π_1/2–X²Σ⁺ band systems of the BaI molecule were recorded by using Fourier transform spectroscopy (FTS). The spectra were produced from the chemiluminescent reaction Ba + I₂ and also by using laser-induced fluorescence (LIF) technique in which the laser sources were a Ti:sapphire single-mode laser, a dye single-mode laser, and a Kr⁺ multimode ion laser. Resolved rotational data, originating from 19 vibrational levels (0 ≤ v ≤ 5 and 7 ≤ v ≤ 19) of the A²Π state, 24 vibrational levels (0 ≤ v ≤ 18 and 20 ≤ v ≤ 24) of the X²Σ⁺ state, and 8 vibrational levels (1 ≤ v ≤ 2 and 9 ≤ v ≤ 14) of the C²Π state, were used in the final analysis. Previously recorded data for the B²Σ⁺–X²Σ⁺ and C²Π–X²Σ⁺ systems, taken from R. F. Gutterres, J. Vergès, and C. Amiot, J. Mol. Spectrosc. 196, 29–44 (1999) and from C. A. Leach, A. A. Tsekouras, and R. N. Zare, J. Mol. Spectrosc. 153, 59–72 (1992), were added to the present work data field. Accurate and improved molecular constants, for the X²Σ⁺, B²Σ⁺, A²Π, and C²Π states, were derived from a simultaneous treatment of the whole data set.     

Oxalyl halides : Analysis of the 3480 Å absorption system of oxalyl chloridefluoride

Oxalyl chloridefluoride (COCl)(COF) exhibits moderately strong discrete absorption in the 3050–3540Å region. The band spectrum has been analyzed as an allowed electronic transition of the planar trans molecule. The most active vibrations are the carbonyl stretching modes ν₁′ and ν₂′ and the in-plane bending mode ν₉. Various other fundamental frequencies in the combining electronic states have been identified. The 0₀⁰ band is at 28 724.5 cm⁻¹; partial rotational analysis confirms that this band is type C. The appearance of “line” structure in the wings of the band is discussed and an explanation offered. The vibrational and rotational analyses confirm that the transition is under the C_s point group, as expected for a singlet-singlet n → π^* type of excitation.     

High-resolution infrared study of the 2ν3 (A1, E) and ν1 + ν3 (E) bands of NF3

The 2ν₃ overtone (A₁, E) and the ν₁ + ν₃ (E) combination bands of the oblate symmetric top ¹⁴NF₃ were studied by FTIR spectroscopy with a resolution of 2.5 × 10⁻³ cm⁻¹. Nearly 500 lines up to K_max/J_max = 30/43 were observed for the weak A₁ component reaching the v₃ = 2⁰ substate (1803.1302 cm⁻¹), the majority of which corresponded to reinforced K = 3p-type transitions. For the strong E component reaching the v₃ = 2^±2 substate (1810.4239 cm⁻¹), about 3550 transitions were assigned up to K_max/J_max = 65/69, favoring a clear observation of the ℓ(4, −2) and ℓ(4, 4) splittings within the kℓ = −2 and +4 sublevels, respectively. The two v₃ = 2 substates are linked by the ℓ(2, 2)- and ℓ(2, −1)-type interactions, providing severe crossings, respectively, at K′ = 6 and near K′ = 24 on the v₃ = 2⁺² side. A model working in the D-reduction and including all these ℓ-type interactions could reproduce together 3695 nonzero weighted experimental data (NZW) through 33 free parameters with a standard deviation of σ = 0.357 × 10⁻³  cm⁻¹. As for the ν₁ + ν₃ (E) combination band, about 3690 lines were assigned up to K_max/J_max = 45/55. Its v₁ = v₃ = 1 upper state (1931.577 5 cm⁻¹) was treated using the same model recently applied to the v₃ = 1 (E, 907.5413 cm⁻¹) state. It yielded 21 free parameters through 3282 NZW experimental data, adjusted with σ = 0.344 × 10⁻³  cm⁻¹ in the D-reduction. For the two excited states, the small and unobserved ℓ(0, 6) interaction was tested as useless. To confirm the adequacy of the vibrationally isolated models used, some other reductions of the Hamiltonian were tried. For the v₃ = 2 state, the D-, L-, and LD-reductions led to similar σ’s, while the Q one was not successful. For the v₁ = v₃ = 1 state, the D- and Q-reductions gave comparable σ’s, while the QD-reduction was not as good. The corresponding unitary equivalence relations are generally more nicely fulfilled for the v₃ = 2 state than for the v₁ = v₃ = 1 state. The three derivable anharmonicity constants in cm⁻¹ are x₃₃ = −4.1528, g₃₃ = +1.8235 and x₁₃ = −7.9652.     

Bd,s– mass-differences from QCD spectral sum rules

We present the first QCD spectral sum rules analysis of the SU(3) breaking parameter ξ and an improved estimate of the renormalization group invariant (RGI) bag constant both entering into the B⁰_d,s– mass-differences. The averages of the results from the Laplace and moment sum rules to order α_s are and

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, in units where f_π=130.7 MeV. Combined with the experimental data on the mass-differences ΔM_d,s, one obtains the constraint on the CKM weak mixing angle |V_ts/V_td|²20.0(1.1). Alternatively, using the weak mixing angle from the analysis of the unitarity triangle and the data on ΔM_d, one predicts ΔM_s=18.6(2.2) ps⁻¹ in agreement with the present experimental lower bound and within the reach of Tevatron 2.     

Hyperfine structure in the BΠ0u state of Br2 and the influence of the perturbing 1u state

Using Doppler-free polarization spectroscopy, the hyperfine structure of the B-X system of ⁷⁹Br₂ was measured for the levels B³Π_0⁺u, v′ = 16–28, and X¹Σ_g⁺, v″ = 1, 2. Besides the nuclear electric quadrupole coupling, the magnetic spin-rotation interaction was analyzed, which varies strongly with the vibrational energy of the electronically excited state. This behavior originates from a perturbing repulsive state Ω = 1_u, the potential of which can be estimated in this way.     

Detection of electric quadrupole transitions in the oxygen A band at 7600 Å

Observations of the sun at low altitude have been used to detect the ^TS (electric quadrupole) branch of the “A” band of atmospheric oxygen at 7600 Å. Line strengths, line-widths, and wavenumbers are tabulated for the eight observable lines, N″ = 5 to 19. These quadrupole transitions are found to be weaker than the main magnetic dipole transitions by a factor of 3 × 10⁻⁶.     

Time-resolved study of the AΠ state of CaH by laser spectroscopy

A time-resolved experiment on the A²Π state of gaseous calcium hydride has been performed by applying laser spectroscopic methods. The following zero-pressure lifetime was obtained for the CaH A²Π state: τ_υ´=0 = 33.2 (±3.2) ns and τ_υ´=1 = 33.7 (±5.2) ns. The lifetime was found to be the same for the A²Π_½ and A²Π_3/2 states.     

Hyperfine coupling constants of NCO in ÃΣ by sub-Doppler spectroscopy

Molecular constants including ¹⁴N hyperfine coupling constants of the NCO radical in the òΣ⁺(000) state have been determined precisely by using the microwave-optical double resonance (MODR) and intermodulated fluorescence (IMF) techniques, where the band was pumped by a dye laser. The results are B = 12 056.559(41), D = 0.0045(16), γ = 22.06(17), b = 430.4(12), c = 80.3(28), and eQq = 2.6(36), all in MHz with one standard error in parentheses. It was found that, because the òΣ⁺ state closely approximates a coupling case (b_βS), MODR did not provide any precise value for the Fermi contact term, but this constant was determined accurately by combining the MODR spectrum with the IMF spectrum.     

New ferromagnetic La3Co2TaO9 double perovskite: Structural and magnetic properties

The new double perovskite La₃Co₂TaO₉ has been prepared by a solid-state procedure. The crystal and magnetic structures have been studied from X-ray powder diffraction (XRPD) and neutron powder diffraction (NPD) data. Rietveld refinements were performed in the monoclinic space group P2₁/n. The structure consists of an ordered array of alternating B′O₆ and B″O₆ octahedra sharing corners, tilted along the three pseudocubic axes according to the Glazer notation a⁻b⁻c⁺. Rietveld refinements show that at RT the cell parameters are a=5.6005(7) Å, b=5.6931(7) Å, c=7.9429(9) Å and β=89.9539(7)°, and the refined crystallographic formula of this “double perovskite” can be written as La₂(Co)_2d(Co_1/3Ta_2/3)_2cO₆. Magnetization measurements and low-temperature NPD data show that the perovskite is a ferromagnet with T_C=72 K. At high T it follows the Curie–Weiss law with an effective magnetic moment of 3.82μ_B per Co ion which is very close to spin only Co²⁺ (HS).     

Band analysis of the Swan system (dΠg-aΠu) of C2 and CC molecules

The emission spectrum of the d³Π_g-a³Π_u system (Swan bands) due to ¹³C₂ and ¹²C¹³C molecules has been obtained in a low pressure hollow cathode discharge through a mixture of argon and benzene containing enriched ¹³C (90%). The spectrum was photographed on a 3.4-m Ebert spectrograph (reciprocal dispersion 0.54 Å mm⁻¹ in the first order). Isotope effect measurements have been carried out to determine the shift between isotopic bands and those emitted by ordinary molecules. The rotational analysis of six ¹³C₂ bands and three bands of ¹²C¹³C has been performed and molecular constants were derived.