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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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.     

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.     

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.     

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.     

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.     

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.     

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.     

Submillimeter-Wave Spectroscopy of CO in the aΠ State

Submillimeter-wave absorption spectrum of CO in electronically excited a³Π state was observed in the 540–830 GHz region by using a phase-locked BWO spectrometer. New rotational transitions up to J = 9–8 in the vibrational excited states up to v = 5 were analyzed accompanied with previous observations in the RF and millimeter-wave regions. A multivibrational states fit among a′ ³Σ⁺ (v = 0–3) and a³Π (v = 0–7) states was performed in order to analyze overall perturbation between the a³Π and a′ ³Σ⁺ states. As a result, the deperturbed rotational parameters were derived precisely to improve the RKR potential.     

Microscopic description of the A(p, π)A + 1 reaction

We have developed a flexible and thoroughly tested computer program for microscopic calculations of proton-induced pion production in nuclei at bombarding energies up to 500 MeV. The model used includes explicitly both the one-nucleon (pionic stripping) mechanism and the resonant p-wave rescattering part of the two-nucleon mechanism. Initial and final state interactions are included through proton-nucleus and pion-nucleus optical model distortions, with careful consideration of the multiple scattering series. The intermediate delta in the two-nucleon mechanism is treated as static with possible inclusion of a local density approximation for the delta-nucleus interaction. We explain the philosophy of the model, detail the parametrization of the microscopic dynamics, and give the formalism for the calculation of experimental observables. We also describe the testing of the computer program and present preliminary results for the ³He(p, π⁺)⁴He reaction.     

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.     

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.     

Robust Estimation of Term Values in High-Resolution Spectroscopy: Application to the eΣu → aΣg Spectrum of T2

In complex molecular spectra the identification of the pair of states corresponding to an observed transition energy is a difficult process. Erroneous assignments are hard to avoid. They cause fundamental difficulties when using least-squares procedures for estimating term values. On the other hand, a robust fitting method has proven extremely helpful for finding erroneous assignments and for obtaining reliable estimates of term values. These facts are demonstrated by applying both procedures to the estimation of term values in the e³Σ⁺_u → a³Σ⁺_g bands of T₂.     

Assignments of the nπ singlet states of p-benzoquinone

The vapor phase fluorescence spectra of p-benzoquinone-h₄ and d₄ are reported and discussed in relation to the assignment of the low lying singlet states. The low temperature, polarized single crystal electronic absorption spectra of p-benzoquinone and several of its isotopic derivatives are reported. From the isotope shifts and band polarizations of the various vibronic origins, a detailed vibronic analysis is offered of the electronic absorption spectrum of p-benzoquinone which indicates a near degeneracy of the ¹A_u and ¹B_1g electronic states.