Laser Excitation Spectroscopy of the Jet-Cooled Methoxy Radical Amidst Hydroxyl Transitions

Abstract

Laser-induced fluorescence excitation spectra of the methoxy radical have been recorded under high resolution in a supersonic jet expansion. The rotational structure associated with the 3¹ ₀ band of methoxy has been identified in the midst of strong overlapping rotational transitions due to the hydroxyl radical in the 32240 - 32580 cm^?1 spectral region. Rotationally-resolved à ²A₁ – [Xtilde] ²E spectra of the 3¹ ₀ band of methoxy have been explicitly assigned using the nomenclature for prolate symmetric top transitions in doublet states.     

The far-infrared laser magnetic resonance spectra of the OD radical in ground and vibrationally excited states

Laser magnetic resonance spectra of the OD radical in low-lying vibrational levels of the X²Π state have been recorded at a variety of wavelengths in the far-infrared. The spectra have been assigned to rotational and fine-structure transitions and fitted to a model Hamiltonian to determine the appropriate molecular parameters for the levels v = 0 to 3. The results are compared with those from previous studies of OD in these vibrational levels.     

Measurement and analysis of the ν2 band of D216O

The rotational structure of the ν₂ band of D₂¹⁶O between 700 and 1550 cm^?1 has been analyzed from spectra recorded with a Fourier transform spectrometer (nominal resolution: 0.1 cm^?1). By applying Watson's reduced Hamiltonian and a least squares method to the set of observed transitions, together with microwave data and the infrared data of Williamson, 22 rotational constants for the ground state and 17 for the upper state have been obtained which predict the positions of more than 700 observed lines with a standard deviation of 0.04 cm^?1.     

High resolution Fourier transform infrared spectroscopy on CH2DI and CHD2I: evaluation of the ground state constants and analyses of the C-I stretching bands ν3

Abstract

The high resolution (0.0010cm^?1) Fourier transform infrared spectra of the partially deuterated methyl iodide molecules CH₂DI and CHD₂1 have been recorded and analysed in the ν₃ band regions around 510cm^?1. The fundamental band ν₃ is associated with the stretching of the C-I bond and the spectra appear therefore as an asymmetric rotor hybrid a/b-type band and hybrid a/c-type band for CH₂DI and CHD₂I, respectively. About 4700 transitions in the case of CH₂DI and about 3900 transitions in the case of CHD₂I have been assigned. The ground state rotational constants of CH₂DI and CHD₂I have been obtained using the ground state combination differences calculated from the assigned ν₃ transitions and 16 microwave transitions from literature. The S reduced Watson's Hamiltonian has been used in the calculations. In addition, the upper state parameters describing the v₃=1 vibrational states of these molecules have been determined. The obtained ground state constants as well as the upper state parameters have been compared to the corresponding constants of the symmetric top species CH₃I and CD₃I     

High resolution FTIR spectroscopy of CH2DF: analysis of the v 3 and v 4 interacting bands

The high resolution (0.004cm^?1) Fourier transform infrared spectrum of the monodeuterated form of methyl fluoride, CH₂DF, has been recorded and analysed in the v ₃ and v ₄ band region around 1420cm^?1. Both bands, coming from A′ symmetry vibrations, have a/b hybrid character, although in v ₃ the b-type component prevails over the a-type. The rotational structure has been analysed using a dyad model including c-type Coriolis coupling and high order vibrational resonance between these states. Accurate upper state molecular parameters and interaction terms have been obtained by fitting about 3270 assigned transitions to Watson's A-reduced Hamiltonian in the I^r representation. In addition, from a simultaneous fit of ground state combination differences coming from this analysis and 42 literature microwave transitions, an improved and more complete set of ground state constants, including three new sextic centrifugal distortion terms (Φ_JK, Φ_KJ and Φ_K), has been derived.     

Absolute line intensities for oxirane in the 11.4 μm spectral region

Absolute individual line intensities of numerous transitions of the fundamental ν₁₅, ν₁₂ and ν₅ bands of oxirane (ethylene oxide, cyc-C₂H₄O) have been measured in the 750–950 cm^?1 region using eight high-resolution Fourier transform spectra recorded at 0.002 cm^?1 resolution and various pressures. These line intensities were least-squares fit using a theoretical model which takes into account the vibration–rotation interactions linking the upper state rotational levels and, therefore, accurate rotational expansions of the transition moments of the ν₁₅, ν₁₂ and ν₅ vibrational bands were derived. Using the coefficients obtained in the fitting, a line list has been generated and used to perform comparisons with the present measurements. Also, comparisons with measurements taken at medium–low resolution of the ν₁₅/ν₁₂/ν₅ system show excellent agreement.     

Rotationally-Resolved Excitation Spectroscopy of the Methoxy Radical in a Supersonic Jet

Abstract

Laser-induced fluorescence excitation spectra of the methoxy radical have been obtained under sufficiently high resolution in a supersonic jet expansion. The rotational structure associated with its origin band has been identified in the midst of strong overlapping rotational transitions due to the hydroxyl radical in the 31490–31700 cm^?1 spectral region. Rotationally-resolved A ²A₁ - X ²E spectra of the 0₀ ⁰ band of methoxy have been explicitly assigned using the nomenclature for prolate symmetric top transitions in doublet states.     

The stretching fundamental bands of 13C2D2

The stretching fundamental bands of the isotopically substituted acetylene ¹³C₂D₂ have been recorded and analysed. The Raman spectra of the Q branch of v ₁ and v ₂, Σ⁺ _g -Σ⁺ _g bands, have been recorded with an instrumental resolution of about 3.0 x 10^?3 cm^?1 using inverse Raman spectroscopy. The infrared spectrum has been recorded in the region between 2350 cm^?1 and 2500 cm^?1 with an instrumental resolution of 4.0 x 10^?3 cm^?1. Transitions belonging to the v ₃, Σ⁺ _u -Σ⁺ _g , fundamental band have been identified and assigned. The vibrational energies and the rotational and centrifugal distortion constants of the excited states of all the observed transitions have been determined. The molecular parameters obtained reproduce the assigned wave-numbers with a standard deviation of the same order of magnitude as the experimental uncertainty.     

Electronic states of C2H6 +

The complete photoelectron spectrum of ethane has been measured in the valence region using Ne, He I, and He II resonance radiation. The resolution of these spectra is sufficient to partially resolve vibronic structure accompanying the transition to the ground ionic state. The similarity of this structure with that obtained from model calculations using the Jahn-Teller theorem strongly suggests that the active vibration in this transition is a doubly degenerate CH₃ deformation mode and that the ground ionic state is a Jahn-Teller split ² E _g state. These experiments suggest a ² A _1g term for the first excited ionic state. The transition to the ² A _2u state of the ion contains evidence for two active vibrations v ₁ (C–H stretch) and v ₃ (C-C stretch).     

The submillimeter-wave spectrum and spectroscopic constants of SO2 in the ground state

The submillimeter-wave spectrum of SO₂ has been recorded with 0.004 cm^?1 resolution in the region 8–90 cm^?1. About 2000 lines were observed, 1500 of which have been assigned to the ground state rotational transitions of ³²SO₂. Molecular constants up to the 10th order have been derived, combining our data with the available microwave data in the literature. SO₂ rotational spectrum line positions up to 90 cm^?1 can be reproduced from these constants, within the experimental accuracy (2 × 10^?4 cm^?1).     

The υ1 fundamental bands of trans- and cis-DONO studied by high-resolution Fourier-transform spectroscopy

The absorption spectrum of deuterated nitrous acid DONO in the region from 2350 to 3000 cm⁻¹ has been recorded at a resolution of 0.003 cm⁻¹ using a Fourier-transform spectrometer. For the first time, 1366 a- and b-type transitions in the υ₁ fundamental band of trans-DONO and 741 b-type transitions in the υ₁ fundamental band of cis-DONO have been assigned. Rotational and centrifugal distortion constants up to sextic order were determined for the v₁ = 1 states of trans- and cis-DONO using non-linear least-squares calculations. Synthetic spectra calculated using the new rovibrational constants obtained for both species reproduce the observed spectra very well. In addition, the infrared transitions of this study were used, together with previously published pure rotational transitions, to determine improved rotational and centrifugal distortion constants of the ground states of trans- and cis-DONO.     

Very high resolution far infrared synchrotron radiation spectrum of methanol-D1 (CH2DOH) in the first three torsional-vibrational modes

In our effort to systematically study the far infrared (FIR) spectra of asymmetrically mono deuterated methanol (CH₂DOH) and thereby obtain the transition wavenumbers with better and better accuracy (Mukhopadhyay, 2016a,b), the complete Fourier transform (FT) spectra from FIR to infrared (IR) vibrational bands (in the range 50–1190 cm⁻¹) have been re-recorded using the Synchrotron Radiation Source at the Canadian Light Sources in Saskatchewan, Canada. The resolution of the spectrum is unprecedented, reaching beyond the Doppler limited resolution as low as about 0.0008 cm⁻¹ with a signal to noise (S/N) ratio is many fold better than that can be obtained by commercially available FT spectrometer using thermal sources (e.g., Globar). Spectra were also recorded beyond 1190 cm⁻¹ to about 5000 cm⁻¹ at a somewhat lower resolution of 0.002–0.004 cm⁻¹. In this report the analysis of the b-type and c-type torsional - rotational spectra in the ground vibrational state corresponding to gauche- (e₁/o₁) to gauche- (e₁/o₁) and gauche- (e₁/o₁) to trans- (e₀) states in the ground vibrational state are reported and an atlas of the wavenumber for about 2500 FIR assigned absorption lines has been prepared. The transitions within a given sub-band are analyzed using state dependent expansion parameters and the Q-branch origins. The data from previous results (Mukhopadhyay, 2016a,b) along with the present work allowed a global analysis yielding a complete set of molecular parameters. The state dependent molecular parameters reproduce the experimental wavenumbers within experimental uncertainty. In addition, the sensitivity of the spectrum allowed observation of forbidden transitions previously unobserved and helped reassignment of rotational angular momentum quantum numbers of some ΔK = ±1, Q-branch transitions in highly excited states recently reported in the literature. To our knowledge the wavenumbers reported in the present work are the most accurate so far reported in the literature and represent the highest resolution spectra for this molecular species.     

Pulsed Doppler-free two-photon spectroscopy of polyatomic molecules

Doppler-free two-photon electronic spectra of a large polyatomic molecule are recorded for the first time with pulsed laser radiation of near Fourier-transform limited bandwidth (Δv～100 MHz). The resolution obtained is sufficient to resolve individual rotational lines. Due to the high density of these rotational transitions a strong Doppler-broadened background is observed, which is, however, subtantially reduced by suitable choice of photon polarizations. Different vibronic bands of benzene (C₆H₆) are investigated and very accurate rotational constants are found.     

Magnetic hyperfine structure and centrifugal distortion in quadrupole spectra of 12CH3I and 13CH3I

Quadrupole spectra of ¹²CH₃¹²⁷I and ¹³CH₃¹²⁷I in the ground vibrational state have been recorded at high resolution (1–2 KHz) using a radiofrequency-microwave double-resonance spectrometer. The magnetic structure of the quadrupole transitions has been resolved and analyzed. Spin-spin and spin-rotation interaction parameters have been determined, together with accurate values of the quadrupole coupling constants and their centrifugal corrections. Comparison with theory is made by using isotopic relations for the two species of iodomethane.     

Microwave spectrum of formic acid and its isotopic species in D, 13C and 18O. Study of Coriolis resonances between ν7 and ν9 vibrational excited states

In the investigation of the 8 → 280 GHz region, 241 and 57 transitions of H¹²COOH and DCOOH, respectively, have been assigned to the ν₇ and ν₉ vibrational states coupled by a strong Coriolis resonance. The numerical analysis based on Watson's theory of centrifugal distortion coupled with the addition of Coriolis interaction allows us to obtain a set of parameters which fits the transitions well. The rotational spectra of the isotopic species HCOOD and DCOOD have also been investigated. In this investigation 55 and 67 transitions have been assigned to the ν₇ and ν₉ vibrational states of these two molecules, respectively. A very weak Coriolis resonance was detected. Two non-rigid independent rotors were thus employed and gave us a set of parameters which fits the transitions quite well. The rotational spectrum of the ground state of H¹²COOH, H¹³COOH, HCOOD, DCOOH, H¹²C¹⁶O¹⁸OH, and H¹²C¹⁸O¹⁶OH have been reinvestigated and a set of improved parameters was obtained for each species.     

High resolution study of the v 7 + v 8 band of ethylene (C2H4) at 1889 cm-1

The v ₇ + v ₈ A-type band of C₂H₄ has been recorded between 1932 and 1847 cm^-1 with a resolution of 0·06 cm^-1. The transitions with K _-1 ? 8> and J ? 2>5 have been assigned. Although slight Coriolis resonances perturb the band, the analysis has been made easy through the use of an elaborate set of asymmetric top computer programmes. The band centre and a set of upper state constants have been obtained. With these constants, 288 observed upper state energy levels have been fitted with a standard deviation of 0·021 cm^-1.

Using very simple expressions, we have predicted all the resonance effects perturbing the levels of ethylene near 2000 cm^-1. This led us to the identification of the v ₄ + v ₈ and v ₈ + v ₁₀ combination bands in low resolution spectra.     

High-Resolution Visible Laser Spectroscopy of Cobalt Monochloride

The electronic spectrum of cobalt monochloride has been investigated from 415 to 725 nm using a laser-ablation/molecular-beam laser-induced fluorescence spectrometer. Two separate electronic systems with origins near 483.3 and 470.3 nm were observed. Data have been recorded for these two transitions at both low and high resolution. These transitions are now characterized as the [20.7]³Φ₄−X³Φ₄ and [21.3]³Φ₄−X³Φ₄ transitions. A low-resolution vibrational analysis and a high-resolution rotational analysis have been carried out for each system, resulting in accurate values for the ground and excited state vibrational spacings and effective rotational constants. In addition, the magnetic hyperfine structure resulting from the spin of the Co nucleus was resolved and the hyperfine constants were determined. Comparison of the CoCl spectrum with that of CoH and CoF has allowed the ground state electron configuration of (core)(10σ)²(4π)⁴(1δ)³(5π)³(11σ)² to be determined. The hyperfine constants support the electron promotion 11σ→12σ for the observed transitions.     

Infrared Spectroscopy of the ν1 Band of Sulfur Tetrafluoride, SF4

Infrared absorption spectra of the ν₁ axial S-F stretching vibrational bands of sulfur tetrafluoride, SF₄, have been recorded and analyzed. A diode-laser jet spectrometer was used to record high-resolution spectra of ³²SF₄, with 87 vibration-rotation lines of the ν₁ fundamental being assigned. Least-squares fitting of the data yielded a precise vibrational band origin, as well as rotational parameters for the upper state. In addition, lower-resolution spectra of a static sample of SF₄ held at room temperature were recorded using a Fourier transform (FTIR) spectrometer. The progressions of prominent features observed in the room-temperature FTIR spectra are attributed to summation bands arising from ν₁ transitions from excited vibrational levels of the low-frequency ν₄ manifold of both ³²SF₄ and ³⁴SF₄.     

Pulsed field ionisation—ZEKE photoelectron spectrum of o-, m- and p-tolunitrile

Pulsed field ionisation—ZEKE photoelectron spectroscopy has been applied to o-, m- and p-tolunitrile in a supersonic jet. The PFI-ZEKE photoelectron spectra of m- and p-tolunitrile show well-resolved anharmonic structures in the low-frequency region, which are assigned to bands due to internal rotational motion of the methyl group in the cation. Level energies and relative transition intensities are reproduced well by a one-dimensional rotor model with a three-fold axis potential. Potential curves for the internal rotation have been determined. For o-tolunitrile, no band due to internal rotation was found in PFI-ZEKE spectrum. It is suggested that the o-tolunitrile cation has the high barrier for internal rotation and the stable conformation that is the same as that in S₁ and S₀. The barrier height and the conformation are compared with other toluene derivatives, and the relation between the electronic character of –CN and the internal rotational motion has been discussed.