Fourier transform spectroscopy of new emission systems of NbN in the visible region

The emission spectrum of NbN has been reinvestigated in the 8000-35 000  cm⁻¹ region using a Fourier transform spectrometer and two groups of new bands were observed. The bands observed in the 18 000-20 000 cm⁻¹ region have been assigned to a new ³Π-X³Δ transition. Three bands with R heads near 19 463.8, 19 659.0 and 19 757.0 cm⁻¹ have been assigned as 0-0 bands of the ³Π₂-X³Δ₃, ³Π₁-X³Δ₂ and ³Π_0±-X³Δ₁ subbands, respectively, of this new transition. Three additional ΔΩ = 0 bands have been observed in the 24 000-26 000  cm⁻¹ region. A 0-0 band with an R head near 25 409.9 cm⁻¹ has been assigned as a ΔΩ = 0 transition having X³Δ₂ as its lower state while two additional bands with heads near 25 518.7 and 25 534.8 cm⁻¹ were found to be ΔΩ = 0 bands having X³Δ₁ as the common lower state. Two of these three bands are perhaps subbands of a ³Δ-X³Δ transition. Most of the excited levels are affected by perturbations.     

The laser-induced fluorescence spectroscopy of CoF in the ultra violet region

The laser-induced fluorescence (LIF) spectrum of jet-cooled CoF has been obtained in the wavelength region of 260-290 nm for the first time. Seventeen vibronic bands were observed and assigned to three types of transition from the ground state to upper states Ω′ = 3, 4, 5 by rotational analysis. A new vibrational transition with the 0-0 band at 34697.22 cm⁻¹ has been assigned as the [34.7]³Γ₅-X³Φ₄ transition and effective equilibrium molecular constants for the upper state have been determined. In addition, lifetime measurements have been carried out for most of the bands under collision-free conditions. On the basis of the spectroscopic data and lifetime measurements, the electronic structures of these possible high-lying electronic states are discussed.     

Near infrared emission spectra of CoH and CoD

New high resolution emission spectra of CoH and CoD molecules have been recorded in the 640 nm to 3.5 μm region using a Fourier transform spectrometer. The bands were excited in a carbon tube furnace by the reaction of cobalt metal vapor and a mixture of H₂ or D₂ with He at a temperature of about 2600 °C. Eight bands were observed for the A′³Φ₄-X³Φ₄ electronic transition of CoD, and five bands for the corresponding transition of CoH. The (0, 0) bands of the A′³Φ₃-X³Φ₃ system were also recorded for both isotopologues, although one of the parity components in the X³Φ₃ sub-state of CoH was found to be perturbed. The A′³Φ₃-X³Φ₄ transition was also observed in our spectrum of CoH. In addition, a new [13.3]4 electronic state was found by observing [13.3]4-X³Φ₃ and [13.3]4-X³Φ₄ transitions in the spectrum of CoD. Analysis of the transitions with ΔΩ = 0, ± 1 provided more accurate values of spin-orbit splittings between Ω = 4 and Ω = 3 components. The ground-state data for both molecules were fitted both to band-constant and Dunham-expansion expressions, and a combined-isotopologue analysis of the X³Φ₄ spin component was carried out using the data for CoH and CoD. The upper states were represented by term values in these analyses because of perturbations, but estimated band constants for them were obtained in separate fits in which ground-state constants were held fixed.     

The vibrational spectrum of thiazole between 600 and 1400 cm revisited: A combined high-resolution infrared and theoretical study

The Fourier transform infrared gas-phase spectrum of thiazole, C₃H₃NS, has been recorded in the 600-1400 cm⁻¹ wavenumber region with a resolution around 0.0030 cm⁻¹. Nine fundamental bands (ν₅(A′) to ν₁₁(A′), ν₁₅(A″), and ν₁₆(A″)) are analysed employing the Watson model. Ground-state rotational and quartic centrifugal distortion constants as well as upper state spectroscopic constants have been obtained from the fits. A detailed analysis of perturbations identified in the ν₁₁(A′) band at 866.5 cm⁻¹ enables a definitive location of the very weak ν₁₀(A′) and ν₁₄(A″) bands at 879.3 and 888.7 cm⁻¹, respectively. The three levels are analysed simultaneously by a model including Coriolis resonance using an ab initio predicted first order c-Coriolis coupling constant; second and higher order Coriolis parameters are determined. Qualitative explanations in terms of Coriolis resonances are given for a number of crossings observed in ν₅(A′), ν₆(A′), and ν₇(A′) at 1383.7, 1325.8, and 1240.5 cm⁻¹, respectively. The rotational constants, anharmonic frequencies, and vibration-rotation constants (alphas, ) calculated by quantum chemical calculations using a cc-pVTZ and TZ2P basis with B3LYP methodology, have been compared with the present experimental data. The rotation constant differences for each vibrational state, from the ground state values, are closer to experiment from the TZ2P calculations relative to those using cc-pVTZ. The values for Δ_J, Δ_JK, Δ_K, δ_J, and δ_K are close to experiment with both basis sets.     

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.     

The laser-induced fluorescence study of AΣ-XΠi band system of CuS

The laser-induced fluorescence excitation spectra of jet-cooled CuS molecules have been recorded in the energy range of 17 200-19 500 cm⁻¹. Fourteen observed vibronic bands have been assigned as three transition progressions: A²Σ⁻ (v′ = 0-4)-X²Π_3/2 (v″ = 0), A²Σ⁻ (v′ = 0-4)-X²Π_3/2 (v″ = 1), and A²Σ⁻ (v′ = 0-3)-X²Π_1/2 (v″ = 0). Spectroscopic constants of both the X²Π ground state and the A²Σ⁻ excited state of ⁶³CuS and ⁶⁵CuS were determined by analyzing their rotationally resolved spectra. Furthermore, the lifetimes of most observed bands were measured for the first time.     

Fourier transform emission spectroscopy of the CΔ-XΦ, DΔ-XΦ, GΦ-XΦ and GΦ-CΔ systems of CoCl

The emission spectrum of CoCl has been recorded in the 2000-23 000 cm⁻¹ region at high resolution. CoCl was made in a carbon tube furnace by heating cobalt metal to a temperature of about 2300 °C as well as in a DC discharge source and the spectra were observed using a Fourier transform spectrometer. The bands observed in the 2000-13 000 cm⁻¹ interval have been classified into four transitions: C³Δ-X³Φ (2500-3600 cm⁻¹), D³Δ-X³Φ (9300-10 030 cm⁻¹), G³Φ-X³Φ (8500-13 000 cm⁻¹) and G³Φ-C³Δ (7400-7900 cm⁻¹) analogous to the near infrared transitions of CoF reported previously [R.S. Ram, P.F. Bernath, S.P. Davis, J. Chem. Phys. 104 (1996) 6949.]. A rotational analysis of a number of vibrational bands of these transitions has been obtained and spectroscopic constants extracted for the low-lying electronic states of CoCl. It is found that the energy levels of CoCl correlate very well with those of CoF and CoH.     

Analysis of some combination-overtone infrared bands of SO3

Several new infrared absorption bands for ³²S¹⁶O₃ have been measured and analyzed. The principal bands observed were ν₁+ν₂ (at 1561 cm⁻¹), ν₁+ν₄ (at 1594 cm⁻¹), ν₃+ν₄ (at 1918 cm⁻¹), and 3ν₃ (at 4136 cm⁻¹). Except for 3ν₃, these bands are very complicated because of (a) the Coriolis coupling between ν₂ and ν₄, (b) the Fermi resonance between ν₁ and 2ν₄, (c) the Fermi resonance between ν₁ and 2ν₂, (d) ordinary l-type resonance that couples levels that differ by 2 in both the k and l quantum numbers, and (e) the vibrational l-type resonance between the A₁^′ and A₂^′ levels of ν₃+ν₄. The unraveling of the complex pattern of these bands was facilitated by a systematic approach to the understanding of the various interactions. Fortunately, previous work on the fundamentals permitted good estimates of many constants necessary to begin the assignments and the fit of the measurements. In addition, the use of hot band transitions accompanying the ν₃ band was an essential aid in fitting the ν₃+ν₄ transitions since these could be directly observed for only one of four interacting states. From the hot band analysis we find that the A₁^′ vibrational level is 3.50 cm⁻¹ above the A₂^′ level, i.e., r₃₄=1.75236(7) cm⁻¹. In the case of the 3ν₃ band, the spectral analysis is straightforward and a weak Δk=±2, Δl₃=±2 interaction between the l₃=1 and l₃=3 substates locates the latter A₁^′ and A₂^′ “ghost” states 22.55(4) cm⁻¹ higher than the infrared accessible l₃=1 E^′ state.     

Fourier transform spectroscopy of NbS

Emission bands attributed to the NbS radical have been observed in the near infrared and visible regions with FTS techniques using an electrodeless 2450 MHz discharge as a source. Transitions within the doublet and quartet manifolds were recorded at high resolution. The present paper gives the first rotational analysis of this molecule. Numerous bands within the doublet and quartet manifolds have been analyzed, resulting in the characterization of seven different electronic states, three in the doublet and four in the quartet manifold. The states have been labeled in analogy with NbO. The analyzed electronic states are: X⁴Σ⁻, C⁴Σ⁻, A′⁴Φ, D⁴Δ, a²Δ, c²Π, and e²Φ. Four additional substates in the doublet manifold have also been analyzed. In all, 27 vibrational sublevels have been included in the analysis, the total number of rotational lines being about 18 000. The positions of the analyzed transitions are: C⁴Σ⁻ → X⁴Σ⁻ near 15 670 cm⁻¹, D⁴Δ → A′⁴Φ near 7740 cm⁻¹, c²Π → a²Δ near 5850 cm⁻¹ and e²Φ → a²Δ near 8500 cm⁻¹. The overall picture is consistent with the corresponding analysis of NbO. However, three energy separations could not be derived from the experimental data in the case of NbS, i.e., the a²Δ− X⁴Σ⁻, A′⁴Φ− X⁴Σ⁻ and a²Δ_5/2-a²Δ_3/2 splittings. These were set to 4992, 5490, and 992 cm⁻¹, respectively, from preliminary ab initio calculations. In this way, a tentative energy level scheme could be drawn. The first order spin-orbit parameter of the A′⁴Φ state was indeterminable from the experimental data and was set to the value 170 cm⁻¹, derived from the same calculations.     

CW-Cavity Ring Down Spectroscopy of the ozone molecule in the 5980-6220 cm region

The absorption spectrum of ozone, ¹⁶O₃, has been recorded in the 5980-6220 cm⁻¹ region by high sensitivity CW-Cavity Ring Down Spectroscopy (α_min ∼ 3 × 10⁻¹⁰ cm⁻¹). This study extends a first investigation with the same experimental set-up limited to the 6030-6090 cm⁻¹ spectral region [M.-R. De Backer-Barilly, A. Barbe, Vl.G. Tyuterev, D. Romanini, B. Moeskops, A. Campargue, J. Mol. Struct. 780-781 (2006) 225-233] where the analysis of two A-type bands was reported, using FTS spectra for complementary information. The spectral extension of the recordings allows not only to enlarge considerably the observed transitions of these two bands, but more importantly, to assign four new bands: the 3ν₂ + 4ν₃,5ν₁ + ν₂ and ν₁ + 2ν₂ + 4ν₃ B-type bands which were considered as dark in our previous report and the 3ν₁ + 3ν₂ + ν₃ A-type band. The high mixing of the observed states approaching the dissociation limit, leads to the breakdown of the polyad structure and ambiguities in the vibrational labelling which are discussed. Finally, 1789 transitions were assigned, and a suitable Hamiltonian model allows reproducing correctly the observations for five of the six observed bands. The list of 1004 experimentally determined energy levels is provided. The determined effective Hamiltonian and transition moment operators were used to generate a list of 5338 transitions given as Supplementary Material. It is interesting to note that the d₅ parameter of the effective transition moment is of great importance to account for the observed intensities of the B-type bands.     

High resolution infrared spectroscopy of [1.1.1]propellane: The region of the ν9 band

The region of the infrared-active band of the ν₉ CH₂ bending mode [1.1.1]propellane has been recorded at a resolution (0.0025 cm⁻¹) sufficient to distinguish individual rovibrational lines. This region includes the partially overlapping bands ν₉ (e′) = 1459 cm⁻¹, 2ν₁₈ (l = 2, E′) = 1430 cm⁻¹, ν₆ + ν₁₂ (E′) = 1489 cm⁻¹, and ν₄ + ν₁₅ (A₂″) = 1518 cm⁻¹. In addition, the difference band ν₄ − ν₁₅ (A₂″) was observed in the far infrared near 295 cm⁻¹ and analyzed to give good constants for the upper ν₄ levels. The close proximities of the four bands in the ν₉ region suggest that Coriolis and Fermi resonance couplings could be significant and theoretical band parameters obtained from Gaussian ab initio calculations were helpful in guiding the band analyses. The analyses of all four bands were accomplished, based on our earlier report of ground state constants determined from combination differences involving more than 4000 pairs of transitions from five fundamental and four combination bands. This paper presents the analyses and the determination of the upper state constants of all four bands in the region of the ν₉ band. Complications were most evident in the 2ν₁₈ (l = 2, E′) band, which showed significant perturbations due to mixing with the nearby 2ν₁₈ (l = 0, A₁′) and ν₄ + ν₁₂ (E′) levels which are either infrared inactive as transitions from the ground state, or, in the latter case, too weak to observe. These complications are discussed and a comparison of all molecular constants with those available from the ab initio calculations at the anharmonic level is presented.     

The lowest frequency vibrational fundamental of disilane: A three-band analysis

The lowest frequency perpendicular fundamental band ν₉ of disilane has been analyzed to investigate torsion mediated vibrational interactions. We report here a three-band analysis involving torsional levels built on the ground state, the ν₉ vibrational fundamental, and ν₃ fundamental. This analysis includes transitions from the far-infrared torsional bands, ν₄, 2ν₄ − ν₄, 3ν₄ − 2ν₄, two perturbation-allowed rotational series from the overtone band 3ν₄ and transitions restricted to −21 ? kΔk ? 21 in the ν₉ fundamental band. An excellent fit to the included data was obtained. Two interactions are identified in this fit, a resonant Coriolis interaction between the ν₉ torsional stack and that of the ground vibrational state and a Fermi interaction between the ν₃ fundamental and the gs. The introduction of the Fermi interaction causes a large change in the barrier height for the ground vibrational state and makes the barrier shape parameter redundant, indicating that the vibrational contributions to the experimental barrier shape are dominant. Such effects have also been observed for ethane and other similar molecules.     

The [20.4]Φ→(1)Δ Green System of LaF

Electronic bands belonging to the [20.4]³Φ→(1)³Δ system have been observed in the emission spectrum of lanthanum monofluoride at high temperature in the presence of the Ar⁺ 457.9-nm laser line: the (0-0), (1-1), (2-2), and (3-3) bands of the ³Φ₄→³Δ₃ subsystem and the (0-0) bands of the ³Φ₃→³Δ₂ and ³Φ₂→³Δ₁ subsystems. Rotational structures which are well developed in these experimental conditions were analyzed. The data were treated using a polynomial expression for the upper levels term-values, directly at equilibrium for ³Φ₄, whereas a previous Hamiltonian matrix representation of the (1)³Δ state was assumed. A Hund's case (a) representation of the [20.4]³Φ state at v=0 was also considered. Perturbations affecting ³Φ₂ levels at v=0 were observed; the energy and rotational constant of the perturbing state and the interaction parameter were estimated.     

Global fit analysis including the ν9 + ν4 − ν4 hot band of ethane: Evidence of an interaction with the ν12 fundamental

The ν₉ fundamental band of ethane occurs in the 12 μm region. It is the strongest band of ethane in a terrestrial window and is commonly used for the identification of ethane in the Jovian planets. The ν₉ + ν₄ − ν₄ band occurs in the same region; neither can be analysed as an isolated band, since both are embedded in the torsional bath of the ground vibrational state. We report here two global fit models including data from both of these bands as well as the ν₃ fundamental and the ν₄, 2ν₄ − ν₄, and 3ν₄ torsional transitions. The first is restricted to −5 ? KΔK ? 15 in the hot band and gives an excellent fit to the included data. Three resonant interactions are identified in this fit—a Coriolis interaction with two resonant cases between the ν₉ torsional stack and that of the ground vibrational state (gs) and a resonant Fermi interaction between the ν₃ fundamental and the gs. Hot band lines with KΔK < −5 are influenced by a fourth perturbation, with a crossing at −11 < KΔK < −10, which has been attributed to an interaction with the ν₁₂ fundamental. A second fit, demonstrating a promising treatment of this interaction, is also presented.     

High-resolution infrared spectra of OOO ozone isotopomer in the range 900-5000 cm: line positions

Continuing the systematic study of ozone high-resolution infrared spectra, we present in this paper the measurements and analyses of line positions for the ¹⁸O¹⁶O¹⁸O isotopomer. In the range 900-5000 cm⁻¹, corresponding to the observed spectra, 15 bands are analysed: ν₁, ν₃, ν₂+ν₃, ν₁+ν₂, 2ν₃, ν₁+ν₃, 2ν₁, ν₂+2ν₃, ν₁+ν₂+ν₃, 3ν₃, 2ν₁+ν₃, ν₂+3ν₃, ν₁+3ν₃, ν₁+ν₂+3ν₃, and 5ν₃. As in the case of ¹⁶O₃, ¹⁸O₃, and ¹⁶O¹⁸O¹⁶O, the analysis of these bands is performed using effective rovibrational Hamiltonians for nine polyads of interacting upper vibrational states. To correctly reproduce all observed transitions, we have to account for resonance perturbations due to 13 “Dark” states: (0 3 0), (0 4 0), (2 1 0), (0 3 1), (1 0 2), (0 4 1), (1 1 2), (3 1 0), (0 3 2), (0 0 4), (3 2 0), (0 1 4), and (0 4 2). We present the range of observed transitions, the results for spectroscopic parameters (vibrational energy levels, rotational and centrifugal distortion constants, and resonance coupling parameters), as well as the statistics for rovibrational energy levels, calculations and measurements. A comparison of observed band centres with those predicted from an isotopically invariant potential function is discussed. The RMS deviation between predicted and directly observed band centres is ≈0.03 cm⁻¹ up to 3000 and ≈0.25 cm⁻¹ for all 16 bands up to 5000 cm⁻¹.     

Fourier transform spectroscopy of NiCl: Identification of the [10.3] Φ7/2 state

This paper reports the observation of the [10.3] ⁴Φ_7/2 electronic state of NiCl. This state is identified for the first time through the analysis of an electronic band near 10168 cm⁻¹, namely the [10.3] ⁴Φ_7/2-A²Δ_5/2 transition. Molecular parameters for the newly identified [10.3] ⁴Φ_7/2 state are presented. Excited NiCl molecules were produced in a King furnace using NiCl₂ heated to 1600 °C. Emission spectra were recorded using the Fourier transform spectrometer associated with the McMath Pierce Solar Telescope at Kitt Peak.     

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.     

Franck-Condon factors and r-centroids of B-X, C-X and C-A band systems of AlO molecule

Using the high resolution Fourier transform spectrometer the B²Σ⁺-X²Σ⁺ band system of AlO molecule has been recorded. The rotational structure of eighteen bands belonging to B²Σ⁺-X²Σ⁺ transition of AlO have been analyzed which led to accurate rotational and vibrational constants of ground and excited states. A few bands, viz. (2, 1), (3, 2), (4, 3), (2, 3), (3, 4), (4, 5), and (5, 6) were analyzed for the first time. Using these constants, the Franck-Condon factors and r-centroids were computed for the bands of B-X, C-X and C-A band systems for the v′ = 0-8; v″ = 0-8 matrix using the method developed by Jarmain and Nicholls. The F-C factors and r-centroids obey the established relationships.     

Infrared combination and difference bands of the NO dimer

The mid-infrared (1500-3800 cm⁻¹) absorption spectrum of gaseous nitric oxide has been studied at low temperature (99 K) with a long absorption path (160 m) in order to observe weak combination, difference, and overtone bands of the NO dimer. About ten new bands were assigned with greater or lesser certainty. Combined with previous results, they lead to a set of 12 secure and 7 tentative vibrational term values for (NO)₂, essentially doubling our knowledge of NO dimer vibrational states. The strongest non-fundamental bands in this region, other than the ν₁ (symmetric N-O stretch) + ν₅ (asymmetric N-O stretch) overtone, involve combinations of ν₅ with ν₃ (intermolecular stretch). Excitation of ν₅ results in increased frequencies for the intermolecular modes ν₂, ν₃, and ν₄. A new value of 155.5 cm⁻¹ was obtained for ν₄, the elusive infrared-inactive out-of-plane fundamental vibration.     

Analysis of the high-resolution infrared spectrum of cyclopropane

The high-resolution infrared spectrum of cyclopropane (C₃H₆) has been measured from 100 cm⁻¹ to 2200 cm⁻¹. In that region we have identified 24 absorption bands attributed to six fundamental bands, five combination bands, three hot bands and 10 difference bands. Long pathlength spectra, up to 32 m, facilitated the identification and analysis of many previously unstudied infrared inactive, and Raman and infrared inactive vibrational states, including direct access to two forbidden fundamental states, ν₄ and ν₁₄. An improved set of constants for the ground vibrational state as well as for the fundamental vibrations ν₇, ν₉, ν₁₀, ν₁₁ are also reported. The spectral resolution of the measurements varied from 0.002 cm⁻¹ to 0.004 cm⁻¹.