Microwave optical double resonance and reanalysis of the CaF AΠr-XΣ band system

A laser excitation spectrum of the (0,0) and (1,1) bands of the CaF A²Π-X²Σ system has been recorded and all 12 rotational branches assigned on the basis of laser induced fluorescence measurements. Microwave optical double resonance (MODR) measurements were also made on several low-J transitions to obtain precise spectroscopic constants of the X²Σ state. The present set of molecular constants for both the A²Π and X²Σ states represent a vast improvement in precision over previously reported values because of the larger number of line position measurements and the use of a more reasonable Hamiltonian. The excellent agreement between the rotational constants derived from the optical and microwave measurements fully validates the assignments. Important derived constants are listed below (in cm⁻¹) with 95% confidence limits in parentheses.     

Rotational analysis of the aΠr-XΣ transition of GaCl

Six bands (0-0, 0-1, 0-2, 1-0, 2-0, 2-1) of ⁶⁹Ga³⁵Cl have been fully analyzed for the a-X transition, yielding equilibrium constants for the a³Π, state.     

Fourier transform spectroscopy of the AΠ-XΣ transition of NH

The A³Π-X³Σ⁻ transition of NH has been observed using a high-resolution Fourier transform spectrometer. The first three vibrational levels in each state were observed and the vibrational, fine structure, and rotational constants obtained.     

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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Analysis of the Δv = 0 sequence of the β(cΦ - aΔ) system of the TiO molecule

Rotational analyses have been performed on the emission spectra of the 0-0, 1-1, 2-2, and 3-3 bands of the β system (c¹Φ - a¹Δ) of the TiO molecule, excited in a microwave discharge through a mixture of helium, oxygen and TiCl₄ vapor. Rotational constants were obtained for all the bands from which the following equilibrium constants were derived. Be^‘=0.52301±0.00008 cm⁻, αe^‘=0.00313±0.0006 cm⁻, re⁻=1.6391±0.0001 AHigher order constants, D_v and H_v, were calculated for the various vibrational levels.     

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.     

A new electronic transition of antimony chloride in the visible region

The emission spectrum of SbCl has been photographed at high resolution in the region 400 to 640 nm. In addition to bands of two previously reported transitions in this region, A₁-X and A₂-X, 36 bands of a new system have been identified. A vibrational analysis has been made with ν₀₀ ≈ 20 679 cm⁻¹, and 7 of the bands have been rotationally analyzed. The electronic transition has ΔΩ = 0 with lower state constants which match published data for the ground state X³Σ⁻(0⁺). The upper state is characterized by the following ¹²¹Sb³⁵Cl molecular parameters: B′₀ = 0.0922 cm⁻¹, D′₀ = 3.1 × 10⁻⁸ cm⁻¹.     

Rotational vibrational analysis of the BΠ (0) - XΣ band system of BrCl and BrCl

24 bands of the B³Π(0⁺) ← X¹Σ⁺ system of ⁷⁹Br³⁵Cl and ⁸¹Br³⁵Cl have been photographed at high resolution. Direct least-mean square fits of the measured line frequencies were made to determine band origins and rotational constants in the ranges 1 ≤ v″ ≤ 7, 2 ≤ v′ ≤ 8. A reiterative procedure was adopted in which the higher order centrifugal distortion constants (D_v, H_v) were constrained to theoretical values calculated from RKR potential curves. The results of the analysis are used to obtain a set of Franck-Condon factors and r-centroids for the B-X system of BrCl.     

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.     

Laser spectroscopy of LaF: Determination of the separation of the singlet and triplet state manifolds

Tunable dye lasers have been used to excite several known transitions in LaF. Resolved fluorescence spectra obtained after excitation of B¹Π-X¹Σ⁺ and C¹Π-X¹Σ⁺ bands showed transitions to both X¹Σ⁺ and a³Δ states. Analysis of the spectra shows that the state is 1432 cm⁻¹ above X¹Σ⁺, is at 1808 cm⁻¹, and there is an Ω = 2 state (probably ¹Δ) at 5478 cm⁻¹. A new 0⁺-X¹Σ⁺ (v = 0) band has been observed in the vicinity of the B¹Π-X¹Σ⁺ 1-0 band. High resolution excitation spectra of both bands have been obtained, term energies and rotational constants calculated, and the Λ-doubling in B¹Π, v = 1 has been studied. The principal constants (in cm⁻¹) obtained from the analyses wereThe assignments of the low lying states are discussed in terms of their electron configurations and are shown to be in accord with predictions of Ligand Field Theory.     

Fourier Transform Emission Spectroscopy of theAΔ–XΠ Transition of SiH and SiD

The emission spectra of theA²Δ–X²Π transition of SiH and SiD have been observed at high resolution using a Fourier transform spectrometer. The molecules were excited in a Si hollow cathode lamp by passing a discharge through a mixture of Ne and a trace of H₂or D₂. The present data, combined with the previous infrared vibration–rotation measurements, have been used to determine improved molecular constants for the ground and excited states of SiH and SiD.     

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.     

Revised molecular constants and term values for the XΠ and BΣ states of OH

An improved set of molecular constants and term values are given for the X²Π (v = 0–13) and B²Σ⁺ (v = 0 and 1) states of the OH radical. They are derived from a fit of previously published laboratory data and additional lines taken from infrared solar spectra recorded on orbit.     

New spectroscopic studies of the Comet-Tail (AΠi-XΣ) system of the CO molecule

In the electronic emission spectrum of the ¹²C¹⁶O⁺ molecule, 11 bands of the Comet-Tail (A²Π_i-X²Σ⁺) system have been recorded and analyzed. Spin splitting in most of the observed lines of the 0-2, 1-0, 2-0, 2-1, 3-0, 4-0, 4-2, 6-0, 7-0, 7-1, and 8-1 bands, comprising nearly 3400 lines, has been recorded under high resolution by conventional spectroscopy. The rotational analysis of bands has been performed by nonlinear least-squares procedures and by means of effective Hamiltonians of Brown et al. and the rovibronic structure parameters have been obtained. The data of bands of the A-X system and earlier analyzed bands of the B-X and B-A systems have been merged together. As a result of this global fit, the state of information about the energy structure has been significantly enlarged for the A state and enlarged and improved for the X state. Also RKR potential curves for both states and Franck-Condon factors as well as r-centroids of the Comet-Tail system of CO⁺ have been calculated.     

New analysis of the Comet-Tail (AΠi − XΣ) system in the CO isotopic molecule

The emission spectra of the 0-2, 4-2, and 6-1 bands of the Comet-Tail (A²Π_i − X²Σ⁺) system in the ¹⁴C¹⁶O⁺ isotopic molecule, comprising nearly 600 lines, have been recorded and analyzed for the first time. The spectra have been photographed under high resolution by using conventional spectroscopy, and it was possible to separate and observe most of the lines of all the 12 branches of this transition. The reduction of the individual bands’ spectra has been performed by nonlinear least-squares procedure and by means of effective Hamiltonians of Brown et al. the rovibronic structure parameters have been obtained. The currently investigated bands of the Comet-Tail system and the earlier analyzed bands of the A − X and B − A systems in the ¹⁴C¹⁶O⁺ molecule have been merged together. The results of this global fit made it possible to derive a new set of the equilibrium molecular constants for the A and X states. Then the RKR potential curve parameters for both A and X states and Franck-Condon factors as well as r-centroids for the A − X transition have been calculated for the ¹⁴C¹⁶O⁺ molecule.     

Fourier Transform Spectroscopy of theYΣ–XΠiTransition of CuO

TheY²Σ⁺–X²Π_inear-infrared electronic transition of CuO was observed at high resolution for the first time. The spectrum was recorded with the Fourier transform spectrometer associated with the McMath–Pierce Solar Telescope at Kitt Peak. The excited CuO molecules were produced in a low pressure copper hollow cathode sputter with a slow flow of oxygen. Constants for theY²Σ⁺states of CuO are:T₀= 7715.47765(54) cm⁻¹,B= 0.4735780(28) cm⁻¹,D= 0.822(12) × 10⁻⁶cm⁻¹,H= 0.46(10) × 10⁻¹⁰cm⁻¹, γ = −0.089587(42) cm⁻¹, γ_D= 0.1272(79) × 10⁻⁶cm⁻¹,b_F= 0.12347(22) cm⁻¹, andc= 0.0550(74) cm⁻¹. ImprovedX²Π_iconstants are also presented.     

High resolution Fourier transform spectrum of GaCl

The electronic emission spectrum of the A³Π₀-X¹Σ⁺ and B³Π₁-X¹Σ⁺ transitions of Gallium monochloride molecule (⁶⁹GaCl) has been recorded on BOMEM DA8 Fourier transform spectrometer at an apodized resolution of 0.035 cm⁻¹. The rotational structure of the 0-0, 1-0, 2-1, and 3-2, bands belonging to A-X and 0-0, 0-1, 1-2, and 0-2 bands belonging to B-X transitions has been analyzed and equilibrium rotational constants for the X¹Σ⁺ and A³Π₀ states have been obtained. For the first time we are able to determine the Λ-doubling constants in the v = 0 and 1 levels of the B³Π₁ state.     

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.     

High-resolution F T spectrum of A2Πr-X2Σ+ band system of MgCl

The emission spectrum of the A ² Π _r -X ² Σ ⁺ band system of MgCl molecule (360–380 nm) has been recorded on BOMEM DA8 Fourier transform spectrometer at an apodized resolution of 0.035 cm⁻¹. The spectra have been excited under flowing conditions in a demountable stainless steel hollow cathode lamp (400 V, 250 mA) containing anhydrous MgCl₂ and Ar. The resulting spectra are very intense and the 0-0, 1-1, 1-0 bands of A ² Π _1/2-X ² Σ ⁺ sub-transition and the 0-0 band of A ² Π _3/2-X ² Σ ⁺ sub-transition have been rotationally analyzed. Improved molecular constants have been derived using a least-squares fit program in which optical data of earlier analyzed 0-1 and 0-2 bands (A ² Π _1/2-X ² Σ ⁺) was also included. The Λ-doubling constants in the v′ = 0, 1 levels of the A ² Π _1/2 sub-state are as expected, i.e. p ₁ > p ₀, where as it is found that the spin-doubling constants of the v″ = 0, 1 and 2 levels of the ground state X ² Σ ⁺, decrease with the increase in v, i.e. γ ₀ > γ ₁ > γ ₂. This is indicative of the presence of some nearby state, influencing the spin-doubling.     

The spectra and structure of indium iodide: The rotational and vibrational constants of the A0 state

The rotational constants of the A0⁺ state of InI are reported for the first time as B_e = 0.038077 cm⁻¹ and α_e = 0.0002373 cm⁻¹, while T_e = 24402.91 cm⁻¹ for the A0⁺-X0⁺ transition. Accurate vibrational constants for both the A0⁺ and X0⁺ states are computed from the derived band origins.