Laser spectroscopy of the B[17.7]8-X8 and C[19.3]9-X8 transitions of holmium monochloride

Several new transitions of holmium monochloride (HoCl) have been studied at high resolution using laser excitation spectroscopy. Two main transitions, B[17.7]8-X8 and C[19.3]9-X8 have been observed and five bands, 0-0, 0-1, 1-0, 1-1, and 2-1 of the B-X transition and three bands, 0-0, 0-1, and 0-3 of the C-X transition have been obtained at high resolution and rotationally analyzed. Among several low lying states observed in dispersed fluorescence was a strong transition from the C state to a state ∼2140 cm⁻¹ above the ground state. Excitation spectra of this transition have shown that there are apparently two states, ∼6 cm⁻¹ apart. Comparison with ligand field theory calculations are consistent with assigning these states to the excited low lying Ho⁺(4f¹¹6s)Cl⁻ configuration. Several other low lying electronic states have been observed in dispersed fluorescence spectra. Although their assignments could not be established, their energies suggest that they are from the Ho⁺(4f¹⁰6s²)Cl⁻ or Ho⁺(4f¹¹6s)Cl⁻ configurations. Rotational constants have been obtained for the B[17.7]8 and C[19.3]9 states and have been used to speculate on the possible electron configurations for these states.     

Laser spectroscopy of the A[16.4]8.5-X7.5, A[16.4]8.5-Y[0.15]8.5, and A[16.4]8.5-Z[0.85]7.5 transitions of dysprosium monochloride

Laser-induced fluorescence spectra have been obtained at low resolution using a laser ablation source and pulsed dye laser, and at high resolution using a Broida oven and cw ring dye laser. Dispersed fluorescence spectra from two different excited states, A[16.4]8.5 and B[15.4]Ω (unknown Ω) (the states are labelled [10⁻³T₀]Ω according to their energy and Ω assignment) showed transitions to the same four low lying electronic states, X7.5, Y[0.15]8.5, Z[0.85]7.5, and an unassigned state at 970 cm⁻¹. High resolution excitation spectra of the A-X 0-0, A-Y 0-0 and 0-1, and A-Z 0-0 and 0-1 transitions were obtained and a global fit to all the data yielded rotational constants for both ¹⁶²Dy³⁵Cl and ¹⁶⁴Dy³⁵Cl. From the band origins, vibrational frequencies of 291 and 284 cm⁻¹ were obtained for the Y[0.15]8.5 and Z[0.85]7.5 states, respectively, suggesting that these two states originate from the Dy⁺(4f¹⁰6s)Cl⁻ configuration. The ¹⁶²Dy-¹⁶⁴Dy and ³⁵Cl-³⁷Cl isotope effects were studied and both indicated a ground state, X7.5, vibrational frequency of ∼230 cm⁻¹ which was reinforced by the observation, in dispersed fluorescence from the B[15.4] state, of a weak transition to a state 233 cm⁻¹ above the ground state. The observed electronic states and their configurational origin are discussed in terms of ligand field theory predictions.     

Laser spectroscopy of holmium monosulphide: Electronic, vibrational and rotational structure of the A[14.79]8.5-X8.5, A[14.79]8.5-W[0.25]7.5 and A[14.79]8.5-V[0.98]7.5 transitions

Laser induced fluorescence spectra of HoS have been obtained using a Broida oven and a ring dye laser. Dispersed fluorescence spectra showed transitions from a common upper state, A[14.79]8.5 to the v = 0 and 1 vibrational levels of three low lying states, labelled X8.5, W[0.25]7.5 and V[0.98]7.5 (the states are labelled [10⁻³T₀]Ω according to their energy and Ω assignment). High resolution excitation spectra were obtained for all six transitions and a rotational analysis yielded the following principal constants, in cm⁻¹, for the X, W and V states, respectively: T₀ = 0, 251.8713(31), 980.6969(37); B_e = 0.121903(42), 0.121729(37), 0.122561(34); ΔG_1/2 = 463.8811(46), 462.9411(45), 461.2084(127). For the A state, T₀ = 14794.6987(28) cm⁻¹ and B₀ = 0.112596(29) cm⁻¹. The three low lying states are shown to arise from the Ho²⁺[4f¹⁰(⁵I₈)6s]S²⁻ configuration in accord with Ligand Field Theory predictions. The atomic origin of each of the three low lying electronic states was determined from the observed resolved hyperfine structure.     

A study of the AΠ-XΣ and BΣ-XΣ band systems of scandium monosulfide, ScS, using Fourier transform emission spectroscopy and laser excitation spectroscopy

Emission spectra of the A²Π_3/2-X²Σ⁺ (0, 1), (0, 0), and (1, 0) bands and the B²Σ⁺-X²Σ⁺ (0, 1), (0, 0), (1, 0), (2, 0), and (3, 1) bands of ScS have been recorded in the 10 000-13 500 cm⁻¹ region at a resolution of 0.05 cm⁻¹ using a Fourier transform (FT) spectrometer. The A²Π_r-X²Σ⁺ (1, 0) band as well as the B²Σ⁺-X²Σ⁺ (0, 0) and (1, 0) bands have been recorded at high resolution (±0.001 cm⁻¹) by laser excitation spectroscopy using a supersonic molecular beam source. The FT spectral features range up to N = 148, while those recorded with the laser cover the “low-N” regions. The lines recorded with the laser exhibit splittings due to the ⁴⁵Sc (I = 7/2) magnetic hyperfine interactions, which are large (∼6.65 GHz) in the X²Σ⁺ state and much smaller in the B²Σ⁺ and A²Π states. The energy levels were modeled using a traditional ‘effective’ Hamiltonian approach, and improved spectroscopic constants were extracted and compared with previous determinations and theoretical predictions.     

Fourier transform emission spectroscopy of the FΔ-XΦ system of TiF

The emission spectra of TiF have been reinvestigated in the 4200-15 000 cm⁻¹ region using the Fourier transform spectrometer associated with the National Solar Observatory at Kitt Peak. TiF was formed in a microwave discharge lamp operated with 2.5 Torr of He and a trace of TiF₄ vapor, and the spectra were recorded at a resolution of 0.02 cm⁻¹. The TiF bands observed in the 12 000-14 000 cm⁻¹ region have been assigned to a new transition, F⁴Δ-X⁴Φ. Each band consists of four sub-bands assigned as, ⁴Δ_1/2-⁴Φ_3/2, ⁴Δ_3/2-⁴Φ_5/2, ⁴Δ_5/2-⁴Φ_7/2, and ⁴Δ_7/2-⁴Φ_9/2. A rotational analysis of the 0-1, 0-0, and 1-0 bands has been obtained and spectroscopic constants have been extracted.     

Laser spectroscopy of the A9-X8 transition of holmium monochloride

Using laser excitation spectroscopy, 18 red-degraded bands belonging to a single electronic transition of holmium monochloride have been observed in the 615-670 nm region. Thirteen of the bands, with vibrational levels 0?v^′?3 and 0?v″?4 have been obtained at high resolution and rotationally analyzed. Observation of the first lines in some of the bands has shown that Ω=8 in the ground state and Ω=9 in the upper state. By analogy with HoF, this transition has been labeled as A9-X8. The Ω=8 assignment for the X state establishes the ground state configuration of HoCl as Ho⁺(4f¹⁰6s²)Cl⁻, in accord with predictions of Ligand Field Theory. From the rotational analysis, the main equilibrium molecular constants of , for the upper state and , for the ground state have been obtained.     

The Electronic Transition Moment Function for the BΠ-XΔ System of TiO

Several vibronic bands associated with v′=0, 1, and 2 for the B³Π-X³Δ transition of TiO have been observed using a dispersed laser induced fluorescence (DLIF) technique. From intensity distributions of the DLIF spectra, the dependence of the electronic transition moment R_e(r) for the B³Π-X³Δ system was determined as a function of the internuclear distance r. For the determination of the R_e(r) function, a merged fit of the observed distributions, the reported radiative lifetimes of three vibrational levels in the B³Π state, and the reported value of R_e(r) for the (0, 0) band were performed; R_e(r) was determined as R_e(r)=1.3723(79)[1−0.316(81)(r−r₀)+2.0(10)(r−r₀)²](r₀=1.6648 Å and 1.5131 Å≤r≤1.8636 Å). The r-dependence of R_e(r) was much smaller than the reported theoretical predictions. The obtained values of R_e(r) were analyzed simultaneously with the hyperfine coupling constants for the X³Δ state and the spin-orbit constants for the X³Δ and B³Π states to assess the ionic and orbital characters. It was found that the r-dependence of R_e(r) could be accounted for by both the configuration interaction in the B³Π state and the polarization in the unpaired 9σ and 4π orbitals.     

Cavity ring down absorption spectroscopy of the BΣ-XΣ transition of YO

The absorption spectrum of the (2, 0) and (2, 1) bands of the B²Σ⁺-X²Σ⁺ transition of YO between 442 and 478 nm were recorded using laser vaporization/reaction with free-jet expansion and cavity ring down laser absorption spectroscopy. Local rotational perturbations have been found for both spin components of the v = 2 level of the B²Σ⁺ state. The observed perturbations could be ascribed to a degenerate perturbing state interacting with the B²Σ⁺ state. Least-squares fit of the observed upper state term values yielded molecular constants for the v = 2 level of the B²Σ⁺ state and the perturbing ²Π state. Earlier ab initio calculations [J. Chem. Phys. 89 (1988) 2160] indicated that the C²Π state is nearby, it is plausible that the C²Π state is the perturbing state.     

Infrared emission studies of the AΣ-XΠ electronic transition of the SiC radical

The gas phase infrared emission spectrum of the A³Σ⁻-X³Π electronic transition of SiC has been observed using a high resolution Fourier transform spectrometer. Three bands ν′ − ν″ = 0-1, 0-0, and 1-0 have been observed in the 2770, 3723, and 4578 cm⁻¹ regions, where the 0-1 and 0-0 bands were observed for the first time. The SiC radical was generated by a dc discharge in a flowing mixture of hexamethyl disilane [(CH₃)₆Si₂] and He. A total of 1074 rotational transitions assigned to the 0-1, 0-0, and 1-0 bands have been combined in a simultaneous analysis with previously reported pure rotational data to determine the molecular constants for SiC in the two electronic states. The principal equilibrium molecular constants for the A³Σ⁻ state are: B_e = 0.6181195(18) cm⁻¹, α_e = 0.0051921(20) cm⁻¹, r_e = 1.8020884(26) Å, and T_e = 3773.31(17) cm⁻¹, with one standard deviation given in parentheses. The effect of a perturbation was recognized between the ν = 4 level of X³Π and the ν = 0 level of A³Σ, and the analysis was carried out to determine the interaction parameter between the two states.     

High-resolution laser spectroscopy of the potassium-argon molecule: The BΣ state

The absorption spectrum of the KAr molecule has been observed with high resolution between 13 032 and 13 077 cm⁻¹ using tunable laser diodes as light sources, a supersonic beam for production of the molecules, and laser-induced fluorescence for detection. In addition, optical-optical double resonance (OODR) experiments have been performed to simplify the spectrum and to get rotational assignment. Altogether, 670 lines due to the transition B²Σ⁺ ← X²Σ⁺ have successfully been assigned with vibrational levels of the B state ranging from v = 0 to v = 6. The corresponding energy values were fitted to the well-known Dunham expansion. In addition, we were able to analyse a local perturbation between the vibrational level v = 1 of the B state and v = 14 of the A²Π_3/2 state. Unexpected extra lines in the OODR spectra are most probably due to a collision-induced population of other levels. For the equilibrium distance and the well-depth of the B state we obtain from the Dunham expansion 7.03 (8) Å and 26.2 (8) cm⁻¹, respectively.     

High-resolution visible laser spectroscopy of HfF

The electronic spectrum of hafnium monofluoride has been investigated from 415 to 725 nm using a laser-ablation/molecular beam laser-induced fluorescence spectrometer. Several electronic systems were observed and data have been recorded at both low and high resolution. High resolution rotational analyses of the [17.4]1.5-X1.5 (0-0), [17.9]2.5-X1.5 (0-0), [19.7]0.5-X1.5 (0-0), [20.0]0.5-X1.5 (0-0), [21.1]2.5-X1.5 (0-0), [22.3]1.5-X1.5 (0-0), and [23.3]0.5-X1.5 (0-0) subbands have been carried out, resulting in accurate values for the ground and excited state effective rotational constants. Furthermore, the rotational analysis of the subbands assigned as [17.4]1.5-X1.5 (1-0) and [17.9]2.5-X1.5 (1-0) allows us to determine values of 589.7569(6) and 588.9076(6) cm⁻¹ for ΔG^′_1/2 [17.4] and ΔG^′_1/2 [17.9], respectively. From dispersed fluorescence data we find that ΔG^′′_1/2=670(13) cm⁻¹ for the ground state and that another low-lying electronic state lies at ∼2850 cm⁻¹. The data also suggests that a second low-lying electronic state lies at ∼5200 cm⁻¹ above the ground state.     

The AB2-XA1 electronic transition of NO2: A rovibronic survey covering 14 300-18 000 cm

More than 250 rotationally resolved vibrational bands of the A²B₂-X²A₁ electronic transition of ¹⁵NO₂ have been observed in the 14 300-18 000 cm⁻¹ range. The bands have been recorded in a recently constructed setup designed for high resolution spectroscopy of jet cooled molecules by combining time gated fluorescence spectroscopy and molecular beam techniques. The majority of the observed bands has been rotationally assigned and can be identified as transitions starting from the vibrational ground state or from vibrationally excited (hot band) states. An exceptionally strong band is located at 14 851 cm⁻¹ and studied in more detail as a typical benchmark transition to monitor ¹⁵NO₂ in atmospheric remote sensing experiments. Standard rotational fit routines provide band origins, rotational and spin rotation constants. A subset of 177 vibronic levels of ²B₂ vibronic symmetry has been analyzed in the energy range between 14 300 and 17 250 cm⁻¹, in terms of integrated density and using Next Neighbor Distribution. It is found that the overall statistical properties and polyad structure of ¹⁵NO₂ are comparable to those of ¹⁴NO₂ but that the internal structures of the polyads are completely different. This is a direct consequence of the X²A₁-A²B₂ vibronic mixing.     

Transition Probabilities in the BΣ-XΣ and the BΣ-AΠ Electronic Systems of MgO

Transition probabilities for the B¹Σ⁺-X¹Σ⁺ and the B¹Σ⁺-A¹Π electronic systems are presented for v=0-4 and J=0-150 in each electronic state. The functional form of the electronic transition moment for the B-X transition is taken from published ab initio results. The B-A moment is assumed to have the same form and is scaled using empirical branching ratio data. The R_e(r) are used with Rydberg-Klein-Rees (RKR) wavefunctions to calculate transition probabilities for v=0-4 and J=0-150. The RKR potentials were calculated based on empirical spectroscopic constants.     

The visible spectrum of rhodium monoxide: RhO and RhO

Spectroscopic observations are reported for rhodium monoxide from hollow-cathode emission and laser-induced fluorescence experiments. Eleven bands of Rh¹⁶O and 10 of Rh¹⁸O, from the [15.8]²Π-X⁴Σ⁻ (b) and [16.0]²Π-X⁴Σ⁻ (b) transitions, have been rotationally analyzed. The ground state constants have been determined as B₀ = 0.4132, λ₀ = −0.58 and γ₀ = −0.102, in cm⁻¹. Rotational and lambda doubling parameters in v = 0, 1, 2, and 3 excited state vibrational levels have also been determined.     

Fourier transform emission spectroscopy of the BΣ-XΣ system of CN

The emission spectrum of the B²Σ⁺-X²Σ⁺ system of CN has been observed at high-resolution using a Fourier transform spectrometer. The rotational structure of a large number of bands involving vibrational levels v = 0-15 of both electronic states has been analyzed, and improved spectroscopic constants have been determined by combining the microwave and infrared measurements from previous studies. Improved spectroscopic constants for vibrational levels up to v″ = 18 in the X²Σ⁺ state and v′ = 19 in the B²Σ⁺ state have been determined by combining the measurements of the 16-13, 18-17, 18-18, 19-15, and 19-18 bands of Douglas and Routly [Astrophys. J. Suppl. 1 (1955) 295-318] and 17-14 and 17-16 bands of Ito et al. [J. Chem. Phys. 96 (1992) 4195] with our data. The band constants obtained have been used to estimate equilibrium ground state constants for CN.     

Fourier transform emission spectroscopy and ab initio calculations on WO

Emission spectra of WO have been observed in the 4000-35 000 cm⁻¹ region using a Fourier transform spectrometer. Molecules were produced by exciting a mixture of WCl₆ vapor and He in a microwave discharge lamp. A ³Σ⁻ state has been assigned as the ground state of WO based on a rotational analysis of the observed bands and ab initio calculations. After rotational analysis, a majority of strong bands have been classified into three groups. Most of the transitions belonging to the first group have an Ω = 0⁺ state as the lower state while the bands in the second group have an Ω′′ = 1 state as the lower state. These two lower states have been assigned as X0⁺ and X1 spin components of the X³Σ⁻ ground state of WO. The third group consists of additional bands interconnected by common vibrational levels involving some very low-lying states. The spectroscopic properties of the low-lying electronic states have been predicted from ab initio calculations. The details of the rotational analysis are presented and an attempt has been made to explain the experimental observations in the light of the ab initio results.     

The BΣ state of the SO radical

Spectra of the B³Σ⁻- X³Σ⁻ transition in SO above the first dissociation limit are recorded using degenerate four wave mixing. These spectra are combined with earlier work involving laser induced fluorescence, absorption spectra and Fourier transform emission spectra, to enable a rotational analysis and deperturbation of vibrational levels of the B state up to v′ = 16. Numerous perturbations were noted within the B³Σ⁻ state, and the origin of these is discussed. In a number of cases, these perturbations can be attributed to interactions with specific other electronic states of SO, such as A³Π, C³Π, d¹Π, and A″ ³Σ⁺.     

High-resolution infrared spectra of bicyclo[1.1.1]pentane

Infrared spectra of bicyclo[1.1.1]pentane (C₅H₈) have been recorded at a resolution (0.0015 cm⁻¹) sufficient to resolve for the first time individual rovibrational lines. This initial report presents the ground state constants for this molecule determined from the detailed analysis of three of the ten infrared-allowed bands, ν₁₄(e′) at 540 cm⁻¹, ν₁₇ (a₂″) at 1220 cm⁻¹, ν₁₈(a₂″) at 832 cm⁻¹, and a partial analysis of the ν₁₁(e′) band at 1237 cm⁻¹. The upper states of transitions involving the lowest frequency mode, ν₁₄(e′), show no evidence of rovibrational perturbations but those for the ν₁₇ and ν₁₈ (a₂″) modes give clear indication of Coriolis coupling to nearby e′ levels. Accordingly, ground state constants were determined by use of the combination-difference method for all three bands. The assigned frequencies provided over 3300 consistent ground state difference values, yielding the following constants for the ground state (in units of cm⁻¹): B₀ = 0.2399412(2), D_J = 6.024(6) × 10⁻⁸, D_JK = −1.930(21) × 10⁻⁸. For the unperturbed ν₁₄(e′) fundamental, more than 3500 transitions were analyzed and the band origin was found to be at 540.34225(2) cm⁻¹. The numbers in parentheses are the uncertainties (two standard deviations) in the values of the constants. The results are compared with those obtained previously for [1.1.1]propellane and with those computed at the ab initio anharmonic level using the B3LYP density functional method with a cc-pVTZ basis set.     

Spectroscopy of nickel chloride: Identification of the [15.0] Π3/2 and [15.0] Δ5/2 states

Vibrational bands belonging to the [15.0] ²Δ_5/2-A²Δ_5/2, [15.0] ²Δ_5/2-X²Π_3/2, and [15.0] ²Π_3/2-X²Π_3/2 electronic transitions of NiCl have been observed in the 14 000-16 000 cm⁻¹ region. The [15.0] ²Δ_5/2 and [15.0] ²Π_3/2 states are identified for the first time. The observed bands have been recorded at high spectral resolution using several techniques, which include intracavity laser spectroscopy (ILS), Fourier transform emission spectroscopy (FTS), and laser induced fluorescence (LIF) spectroscopy. For the ILS absorption spectra, NiCl molecules were produced in a nickel hollow cathode operated with a small amount of CCl₄. For the FTS emission spectra, excited NiCl molecules were produced in a King-type carbon tube furnace loaded with NiCl₂ and heated to 1600 °C. In the LIF work, NiCl molecules were produced by reacting laser-ablated nickel with PCl₃ seeded in argon. Detailed analysis of rotational transition lines indicates that the observed [15.0] ²Δ_5/2 and [15.0] ²Π_3/2 states are only separated by 10 cm⁻¹ and are interacting with each other. Molecular constants for these newly observed electronic states are reported.     

High resolution infrared spectroscopy of [1.1.1]propellane

The infrared spectrum of [1.1.1]propellane has been recorded at high resolution (0.002 cm⁻¹) with individual rovibrational lines resolved for the first time. This initial report presents the ground state constants for this molecule determined from the analysis of five of the eight infrared-allowed fundamentals ν₉(e′), ν₁₀(e′), ν₁₂(e′), , as well as of several combination bands. In nearly all cases it was found that the upper states of the transitions exhibit some degree of perturbation but, by use of the combination difference method, the assigned frequencies provided over 4000 consistent ground state difference values. Analysis of these gave for the parameters of the ground state the following values, in cm⁻¹: B₀ = 0.28755833(14), D_J = 1.1313(5) × 10⁻⁷, D_JK = −1.2633(7) × 10⁻⁷, H_J = 0.72(4) × 10⁻¹³, H_JK = −2.24(13) × 10⁻¹³, and H_KJ = 2.25(15) × 10⁻¹³, where the numbers in parentheses indicate twice the uncertainties in the last quoted digit(s) of the parameters. Gaussian ab initio calculations, especially with the computed anharmonic corrections to some of the spectroscopic parameters, assisted in the assignments of the bands and also provided information on the electron distribution in the bridge-head carbon-carbon bond.