A High-Resolution Fourier Transform Infrared Study of the ν3, ν4, and ν5 Bands of Deuterated Formyl Chloride (DCOCl)

High-resolution infrared spectra of the low-lying ν₃, ν₄, and ν₅ fundamentals of the transient molecule DCOCl are reported. These type-A/B hybrid bands have been analyzed in detail, providing extensive rotational assignments for the DCO³⁵Cl and DCO³⁷Cl isotopomers. The ground state constants have been refined by a simultaneous fit of the available microwave data and FTIR combination differences from the three bands. The excited state constants have been determined by fitting assignments over a wide range of J and K_a values. A small perturbation was found at high K_a values in the ν₄ band and determined to be due to a ΔK_a = −2 interaction with the rotational levels of the 6¹ vibrational state.     

Double resonance and collision-induced transitions in the radiofrequency spectra of H2CO and HDCO observed inside the cavity of a CO2 laser

Many radiofrequency resonances corresponding to transitions between the two components of a K-type doublet in H₂CO and HDCO have been observed using infrared-radiofrequency double resonance inside a CO₂ laser cavity. For strong resonances, additional transitions induced by collisions have also been observed and these provide information on collisional processes. The collision-induced transitions also provide a method for assigning the K doublet frequencies in the ground and v₄ = 1 states of H₂CO, and in the ground, v₅ = 1, and v₆ = 1 states of HDCO; the rovibrational transitions pumped by the CO₂ laser can therefore be determined. The upper state rotational transitions and the infrared frequencies for the transitions in exact coincidence with the CO₂ laser lines provide accurate additional data in the analysis of the conventional infrared spectrum of the ν₅ and ν₆ bands of HDCO. In addition, the 195-μm far-infrared laser line in HDCO, observed by Dangoisse et al. [J. Quantum Electron. QE-13, 730–731 (1977)] has been assigned as the 24_6,19→23_6,18 transition in the v₆ = 1 state.     

The far-infrared spectrum and spectroscopic parameters of PH3 in the ground state

The far-infrared spectrum of phosphine, PH₃, was recorded in the region between 30 and 200 cm⁻¹ at a resolution of 0.002 cm⁻¹. ΔJ = +1, ΔK = 0 rotational transitions in the ground state were measured and assigned up to J″ = 22 and K = 19. These transitions were analyzed together with the presently available microwave and submillimeter-wave data on the basis of different formulations of the rotational Hamiltonian, which included Δk = ±3 and/or Δk = ±6 interaction terms. An upper limit for the constant of the inversion splitting was obtained by fitting the same transitions to an appropriate inversion-rotational Hamiltonian. Rotational transitions in the v₂ = 1 and v₄ = 1 vibrational states were also observed.     

Fourier transform emission spectroscopy of the TiF radical in the 407 nm region

Ultraviolet emission spectra of the TiF radical in the 407 nm region have been observed at a resolution of 0.04 cm⁻¹ using a Fourier transform spectrometer. A new electronic assignment of ⁴Γ–X⁴Φ has been proposed. Rotational analysis has been obtained for the 0–0 and 1–1 vibrational bands of the ⁴Γ_5/2–X⁴Φ_3/2, ⁴Γ_9/2–X⁴Φ_7/2, and ⁴Γ_11/2–X⁴Φ_9/2 subbands and the 0–0 band of ⁴Γ_7/2–X⁴Φ_5/2. The lower state rotational and centrifugal distortion constants are consistent with the previous results [J. Mol. Spectrosc. 184 (1997) 186; J. Chem. Phys. 119 (2003) 9496], to the conformation that the lower state of the 407 nm band is the ⁴Φ ground electronic state. Rough estimates of the vibrational interval ΔG(1/2) and the spin–orbit coupling constant A in the ⁴Γ state were also obtained.     

Fourier transform infrared spectrum of the ν3 band of HCO

The ν₃ fundamental band of the formyl radical, HCO, in the 5.3-μm region has been observed at high resolution (0.0025 cm⁻¹, unapodized) using a Fourier transform spectrometer. The HCO radicals were formed by the reaction of F atoms with H₂CO in a fast-flow multiple-traversal absorption cell. A total of 298 lines were measured with an accuracy of about 0.0004 cm⁻¹ and assigned to transitions with values of the rotational quantum numbers N and K_a up to 20 and 5, respectively. These data greatly improve the knowledge of the HCO ν₃ line positions and (v₁v₂v₃) = (001) vibrational state molecular parameters as compared to earlier laser magnetic resonance studies of this band, especially for higher values of N. The ν₁ fundamental band of HCO was also observed and an analysis of these data agrees well with the recent study of Dane et al. [J. Chem. Phys. 88, 2121–2128 (1988)].     

Velocity modulation spectroscopy of molecular ions I: The pure rotational spectrum of TiCl (XΦr)

The pure rotational spectrum of the TiCl⁺ ion in its X³Φ_r ground state has been measured in the frequency range 323-424 GHz, using a combination of direct absorption and velocity modulation techniques. The ion was created in an AC discharge of TiCl₄ and argon. Ten, eleven, and nine rotational transitions were recorded for the ⁴⁸Ti³⁵Cl⁺, ⁴⁸Ti³⁷Cl⁺, and ⁴⁶Ti³⁵Cl⁺ isotopomers, respectively; fine structure splittings were resolved in every transition. The rotational fine structure pattern was irregular with the Ω = 4 component lying in between the Ω = 2 and 3 lines. This result is consistent with the presence of a nearby ³Δ_r state, which perturbs the Ω = 2 and 3 sub-levels, shifting their energies relative to the Ω = 4 component. The data for each isotopomer were analyzed in a global fit, and rotational and fine structure parameters were determined. The value of the spin-spin constant was comparable to that of the spin-orbit parameter, indicating a large second-order spin-orbit contribution to this interaction. The bond length established for TiCl⁺, r₀ = 2.18879 (7) Å, is significantly shorter than that of TiCl, which has r₀ = 2.26749 (4) Å. The shorter bond length likely results from a Ti²⁺Cl⁻ structure in the ion relative to the neutral, which is thought to be represented by a Ti⁺Cl⁻ configuration. The higher charge on the titanium atom shortens the bond.     

Diborane : High resolution infrared rovibration studies of B2H6 and B2D6

Ground state rotation and quartic distortion constants were obtained for ¹¹B₂D₆ from the analysis of high resolution (0.05 cm⁻¹) Fourier transform infrared spectra. The bands studied comprised the ν₁₇, ν₁₈ type A, and ν₁₄, ν₉ + ν₁₅ type C bands of ¹¹B₂H₆ and the ν₁₆, ν₁₇, ν₁₈ type A, ν₈ type B, and ν₁₄ type C bands of ¹¹B₂D₆. In the case of ¹¹B₂H₆, the authors' ground state data were combined with those of Lafferty et al. obtained from a previous study (J. Mol. Spectrosc. 33, 345–367 (1970)) at comparable resolution of the ν₁₆ type A and ν₈ type B fundamentals. Information on the ground state rotational energy manifold of ¹¹B₂H₆ was accumulated up to J = 23, K_a = 18, and of ¹¹B₂D₆ up to J = 32, K_a = 22. This permitted rather precise determination of the distortion constants Δ_J⁰, Δ_JK⁰, Δ_K⁰, although δ_J⁰ and δ_K⁰ proved to be too small (< 10⁻⁷ cm⁻¹) and were constrained to values calculated from the force field. Sets of upper state parameters were determined for all vibrational levels studied. Although these appear to be essentially unperturbed globally, several localized perturbations were observed and identified.     

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.     

High resolution laser spectroscopy of the titanium monohalides, TiCl and TiBr

The electronic spectra of the titanium monohalides, TiCl and TiBr, have been investigated in the blue-violet region using a laser ablation molecular beam spectrometer. Five subbands assigned as ⁴Γ_5/2-X⁴Φ_3/2 (0, 0), ⁴Γ_5/2-X⁴Φ_3/2 (1, 1), ⁴Γ_5/2-X⁴Φ_5/2 (0, 0), ⁴Γ_7/2-X⁴Φ_5/2 (0, 0) and ⁴Γ_7/2-X⁴Φ_7/2 (0, 0) were observed and recorded at both low and high-resolution for titanium monochloride. A Hund’s case (a) rotational analysis has been carried out for the ⁴⁸Ti³⁷Cl and ⁴⁸Ti³⁵Cl isotopic species, and polynomial analyses for these, as well as the ⁴⁶Ti³⁵Cl, ⁴⁷Ti³⁵Cl, ⁴⁹Ti³⁵Cl, and ⁵⁰Ti³⁵Cl isotopologues have been completed. The same spectral region yielded several molecular transitions for titanium monobromide, 10 of which were recorded at high resolution. Six of these have been attributed to a ⁴Γ-X⁴Φ electronic transition at 23 484 cm⁻¹, while the remaining four have been assigned to a second ⁴Γ-X⁴Φ electronic transition at 23 613 cm⁻¹. A Hund’s case (a) global analysis has been carried out for the ⁴⁸Ti⁷⁹Br and ⁴⁸Ti⁸¹Br isotopologues.     

Laser magnetic resonance of the O2 molecule at 699 μm

A new highly sensitive far infrared optically pumped laser magnetic resonance (LMR) spectrometer has facilitated the observation of 21 transitions in O₂ at 699 μm (428.6285 GHz). All of these transitions involve N = 3 ← 1 of the oxygen molecule in its electronic ground state, X³Σ_g⁻. Of these 21 lines, 10 are due to the ¹⁶O₂, v = 0; 5 are due to the ¹⁶O₂, v = 1; 5 are due to the ¹⁶O¹⁸O, v = 0; and 1 set of 6 hyperfine components is due to the ¹⁶O¹⁷O, v = 0. From the intensity of the observed lines the sensitivity limit of this LMR spectrometer is found to be about 10⁻⁹ cm⁻¹ at this frequency with a 1-sec time constant.     

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).     

Analysis of the nuclear quadrupole interaction of Disulfur Dichloride, S2Cl2

Pure rotational spectra of S₂³⁵Cl₂ and S₂³⁵Cl³⁷Cl have been observed using a Fourier-transform microwave spectrometer. An analysis of the hyperfine structure made by considering the nuclear spin statistics showed that S₂Cl₂ has C₂symmetry, where the hyperfine splittings due to the two Cl nuclei were analyzed precisely. The nuclear quadrupole coupling constants including the off-diagonal (χ_ab, χ_ac, χ_bc) components and the nuclear spin–rotation interaction constants associated with the two Cl nuclei have been determined for the first time. We have shown that the nuclear quadrupole interaction plays an important role in the ortho–para mixing.     

Vibration-inversion-rotation spectra of ammonia: Centrifugal distortion, Coriolis interactions, and force field in NH3, NH3, ND3, and NT3

An effective inversion-rotation Hamiltonian has been developed for NH₃ which avoids the necessity of having to include high powers of the inversion motion coordinate in the Taylor expansions of the potential energy and the inverse moment of inertia tensor. This nonrigid bender Hamiltonian describes the centrifugal distortion and the Coriolis interactions in the ground and excited inversion states. It also describes the inversion doublings in the ground and excited vibration-inversion states of ammonia. A least-squares procedure that includes the numerical integration of the Schrödinger wave equation has been used to determine the harmonic force field and the double-minimum inversion potential function for (¹⁴NH₃, ¹⁵NH₃) and for (¹⁴ND₃ and ¹⁴NT₃).The anomalous rotational dependence of the inversion doublings in the (±l) components of the v₄ = 1 state of ¹⁴NH₃ has been explained by the Coriolis interactions between v₂=1, v₄ = 1, v₂ = 2, v₂ = 1, v₄ = 1, and v₂ = 3 vibration-inversion states.     

The rotational spectrum of 13C2HD in the ground and excited bending states

The pure rotational spectrum of ¹³C₂HD was recorded in the range 100–700 GHz. Lines belonging to the ground vibrational state were observed from J^″ = 1 to J^″ = 11. Several absorption lines were also detected in the bending states v₄ = 1 (Π), v₅ = 1 (Π), v₄ = 2 (Σ⁺ and Δ), v₅ = 2 (Σ⁺ and Δ), v₄ = v₅ = 1 (Σ^?, Σ⁺ and Δ), v₄ = 3 (Π and Φ) and v₅ = 3 (Π and Φ). The transition frequencies measured in this work were fitted together with all the infrared lines available in the literature. The global fit allowed a very accurate determination of the vibrational, rotational and ?-type interaction parameters for the bending states of this molecule.     

Infrared combination bands of CH4 in crystal fields

Overtone and combination bands were observed between 1000 and 5000 cm^–1 for CH₄ molecules in several crystal fields: solid phases I and II, and diluted alloys with Kr. In the anisotropic field of phase II, a full (rotation/libration)-vibration spectrum was observed in the combination bands 2v ₄,v ₂+v ₄, andv ₃+v ₄. Here, all lines could be assigned to transitions of either D_2d or O_h molecules. The structure ofv ₃–v ₄,v ₂+2v ₄,v ₁+v ₄,v ₂+v ₃ and 3v ₄ bands could not be resolved. In phase I, all spectra show the characteristic features of rotational diffusion, while in a Kr matrix a rotovibrational structure could again be observed in the overtone and combination bands.     

The sub-millimeter and Fourier transform microwave spectrum of HZnCl (X Σ)

The pure rotational spectrum of HZnCl (X ¹Σ⁺) has been recorded using sub-millimeter direct-absorption methods in the range of 439–540 GHz and Fourier transform microwave (FTMW) techniques from 9 to 39 GHz. This species was produced by the reaction of zinc vapor and chlorine gas with H₂ or D₂ in a d.c. glow discharge for the sub-millimeter studies. In the FTMW measurements, HZnCl was created in a discharge nozzle from Cl₂ and (CH₃)₂Zn. Between 5 and 10 rotational transitions were measured in the sub-millimeter regime for four zinc and two chlorine isotopologues; four transitions were recorded with the FTMW machine for the main isotopologue, each consisting of several chlorine hyperfine components. The data are consistent with a linear molecule and a ¹Σ⁺ ground electronic state. Rotational and chlorine quadrupole constants were established from the spectra, as well as an r_m⁽²⁾ structure. The Zn–Cl and Zn–H bond lengths were determined to be 2.0829 and 1.5050 Å, respectively; in contrast, the Zn–Cl bond distance in ZnCl is 2.1300 Å, longer by 0.050 Å. The zinc–chlorine bond distance therefore shortens with the addition of the H atom. The ³⁵Cl electric quadrupole coupling constant of eQq = −27.429 MHz found for HZnCl suggests that this molecule is primarily an ionic species with some covalent character for the Zn–Cl bond.     

The rotational-vibrational spectra of HNCS and DNCS : An analysis of the high resolution spectra

Ro-vibrational spectra of HNCS and DNCS have been obtained in the spectral range 300–4000 cm⁻¹ with a practical resolution limit of 0.06 cm⁻¹ in the region 350–1200 cm⁻¹ and 0.15 cm⁻¹ in the region 1200–4000 cm⁻¹. The observed fine structure permitted definitive assignments for some of the ^PQ_K, ^QQ_K, and ^RQ_K branches in both molecules, and yielded sets of rotational constants in substantial agreement with those obtained from recent microwave and far-infrared studies. Precise estimates of the band origins have been obtained and there is evidence of second-order Coriolis coupling between the three bending modes in each molecule. The isolation of the out-of-plane bending modes has lead to a re-assignment of ν₃, ν₄, ν₅, and ν₆ for each molecule. The band origins, uncorrected for Coriolis interaction, are for HNCS and DNCS, respectively. v₁:3538.6 ±0.3, 2644.5±0.5cm⁻¹;v₂:1989.0 ±0.3, 1944.3±0.5cm⁻¹;v₃:857.0 ±0.6, 851.0±0.1cm⁻¹;v₄:615.0 ±0.5, 549.1±0.2cm⁻¹;v₅:469.2 ±0.1, 365.8 ±0.2cm⁻¹;v₆:539.2 ±0.5, 481.0±0.1cm⁻¹;     

Rotational spectra of DCCCN in some excited vibrational states

We have observed and analyzed the millimeter-wave spectrum of deuterated cyanoacetylene (DCCCN) in 12 excited vibrational states. The Hamiltonian of K. M. T. Yamada, F. W. Birss, and M. R. Aliev (J. Mol. Spectrosc. 112, 347–356 (1985)) has allowed the determination of accurate rotational and l-type doubling constants for the following isolated states: (v₄, v₅, v₆, v₇) = (1001), (0001), (0002), (0003), (0010), (0100), (0101), (0011), and 0012). The anharmonic resonance between the (1000), (0020), and (0004) states has been observed and analyzed, yielding the unperturbed rotational constants and the Fermi interaction constant.     

Velocity modulation spectroscopy of molecular ions II: The millimeter/submillimeter-wave spectrum of TiF (XΦr)

The pure rotational spectrum of the molecular ion TiF⁺ in its ³Φ_r ground state has been measured in the range 327-542 GHz using millimeter-wave direct absorption techniques combined with velocity modulation spectroscopy. TiF⁺ was made in an AC discharge from a mixture of TiCl₄, F₂ in He, and argon. Ten transitions of this ion were recorded. In every transition, fluorine hyperfine interactions, as well as the fine structure splittings, were resolved. The fine structure pattern was found to be regular with almost equal spacing in frequency between the three spin components, in contrast to TiCl⁺, which is perturbed in the ground state. The data were fit with a case (a) Hamiltonian and rotational, fine structure, and hyperfine constants were determined. The bond length established for TiF⁺, r₀ = 1.7775 Å, was found to be shorter than that of TiF, r₀ = 1.8342 Å—also established from mm-wave data. The hyperfine parameters determined are consistent with a δ¹π¹ electron configuration with the electrons primarily located on the titanium nucleus. The nuclear spin-orbit constant a indicates that the unpaired electrons are closer to the fluorine nucleus in TiF⁺ relative to TiF, as expected with the decrease in bond length for the ion. The shorter bond distance is thought to arise from increased charge on the titanium nucleus as a result of a Ti²⁺F⁻ configuration. A similar decrease in bond length was found for TiCl⁺ relative to TiCl.     

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.