Determination of the molecular dipole moment of bromofluoromethane: Microwave Stark spectra and ab initio calculations

The electric dipole moment of bromofluoromethane, CH₂⁷⁹BrF, has been determined with a good accuracy by observing the second order ΔM_J = 0 Stark spectrum of the J = 3_2,1 ← 3_1,2, J = 5_2,3 ← 5_1,4 and J = 5_2,4 ← 5_1,5 rotational transitions. In addition, the equilibrium geometry and dipole moment have been evaluated using highly accurate ab initio calculations. By comparing the experimental [μ_a = 0.3466(11) D and μ_b = 1.704(26) D] and theoretical [μ_a = −0.339 D and μ_b = −1.701 D] dipole moment components, a very good agreement has been found.     

The torsion-rotation spectrum of perchloric acid, HClO4

The rotational spectrum of HClO₄ has been observed in selected regions between 51.7 and 870 GHz. The molecule is a near spherical rotor with a moderately low barrier to internal rotation. The spectrum is characterized by strong μ_a, R-branch groupings with B + C = 5276.78 MHz. Although there are no E torsional states, the R-branches show three distinct groups of lines. There is a relatively tight cluster of symmetric rotor like transitions with K = 3n, a rather regular progression of transitions with K = 3n + 2 to high frequency and a less regular group of transitions with K = 3n + 1 to low frequency. Because the molecule is nearly spherical, the energy as a function of K is dominated by the K dependent solutions of the Mathieu equation. This unusual energy level distribution gives rise to numerous anomalous splittings and shifts due to avoided crossings within the K stacks as well as widely scattered μ_b transitions. The fitting procedure will be described and the effective parameters will be presented. Rotational transitions of excited torsional states at and above the top of the barrier and the v_t = 2-0 far infrared spectrum have been assigned. The dipole moment and the quadrupole coupling constants have been determined. Structural implications will be discussed.     

Microwave and sub-mmwave study of CH3SiH3 including the perturbation-allowed torsion-vibration difference band (ν12=0,ν6=3)↔(ν12=1,ν6=0)

The vibration-torsion-rotation Hamiltonian in CH₃SiH₃ has been investigated using Fourier transform microwave methods and tunable sideband far-infrared spectroscopy. Four different studies have been carried out. First, the Q-branch of the torsion-vibration difference band (ν₁₂=0,ν₆=3)↔(ν₁₂=1,ν₆=0) has been measured between 17.8 and 26.6 GHz. When three quanta of the torsional mode ν₆ are excited in the ground vibrational state (gs) for (σ=−1) torsional sublevels with K=6, these transitions become allowed through resonant Coriolis-like coupling to the lowest lying degenerate mode ν₁₂ with no quanta of ν₆ excited. Second, direct l-doubling transitions in the state (v₁₂=1, v₆=0) have been observed between 8.3 and 17.5 GHz for both torsional sublevels σ=0 and σ=±1. In the limit that the intervibrational interactions vanish, the σ-splitting between lines of the same J would be difficult to resolve, but frequency differences of more than 1 GHz due to these interactions have been determined. Third, the (J=1←0) spectrum just below 22 GHz has been re-measured with higher resolution for 0?v₆?4 in the gs and for (v₆=0) in ν₁₂. Finally, the (J=45←44) spectrum near 1 THz has been obtained for 0?v₆?2 in the gs. A global data set of 3423 frequencies has been formed by merging the present 123 measurements with the data set used recently in the simultaneous analysis of the ν₁₂ and ν₅ bands by Schroderus et al. [J. Chem Phys. 115 (2001) 1392]. By refining the (gs/ν₁₂/ν₅) Hamiltonian developed in this earlier work in which the torsional motion is grouped with the vibrational degrees of freedom, a good fit to within experimental error has been obtained by varying 45 parameters. A fit of comparable quality has also been obtained using a similar analysis in which the torsional motion is grouped with the rotational degrees of freedom. The values of the molecular constants determined in the two models are compared.     

Rotational spectra of quinoline and of isoquinoline: spectroscopic constants and electric dipole moments

Rotational spectra of quinoline and of isoquinoline have been observed in the centimeter- and millimeter-wave regions. The spectra were assigned on the basis of bands formed by high-J transitions, which were measured up to J″?128 and ν?234 GHz. Complementary measurements were also made on low-J, centimeter-wave spectra observed in supersonic expansion and with fully resolved nuclear quadrupole hyperfine structure. Accurate rotational, centrifugal distortion and hyperfine splitting constants for the ground states of both molecules are reported. The electric dipole moments for the two molecules were also determined from Stark effect measurements and are μ_a=0.14355(19), μ_b=2.0146(17), μ_tot=2.0197(17) D for quinoline, and μ_a=2.3602(21), μ_b=0.9051(14), μ_tot=2.5278(20) D for isoquinoline. The experimental observables were found to be rather accurately predicted by MP2/6-31G** ab initio calculations, and corresponding molecular geometries are also reported.     

Analysis of the pure-rotational spectrum in the ν28 = 1 excited torsional state and torsional couplings of trans-ethyl methyl ether

The trans-ethyl methyl ether molecule has three low-lying torsional modes, that is, two inequivalent methyl internal rotations and an asymmetric skeletal torsion. The internal rotations of the CCH₃ and OCH₃ methyl rotors and the skeletal torsion correspond to the vibrational modes, ν₂₈, ν₂₉ and ν₃₀ respectively. In this study, the microwave absorption spectrum in the ν₂₈ = 1 CCH₃ torsional state was analyzed for the first time. Nine hundred fifty seven lines up to J = 48 and K = 4 were assigned, and the rotational, centrifugal distortion and internal rotational tunneling parameters were determined with the use of a tunneling matrix formalism. By combining the present results on the ν₂₈ = 1 torsional state with those for the ν₃₀ = 1 skeletal torsional state and the ν₂₉ = 1 OCH₃ torsional state, torsional couplings are estimated in order to understand quantitatively the inverted A/E sequence patterns observed for those three excited torsional states.     

The millimeter wave rotational spectrum of pyruvic acid

The rotational spectrum of pyruvic acid has been investigated for the first time in the millimeter-wave region, at 160-314 GHz, and also in supersonic expansion, at 10-17.4 GHz. The analysis of the broadband spectra recorded in this work was carried out with the newly developed AABS software package for Assignment and Analysis of Broadband Spectra, and precise spectroscopic constants are reported for the ground state, the first excited state of the low-frequency skeletal torsional mode ν₂₄, and the first excited state of the methyl torsional mode ν₂₃. Limited results have also been obtained for several higher excited states. The dataset for the ground state currently exceeds 1500 lines and for both the A and E internal rotor sublevels spans the complete range of values of K_a at the mid values of J for the measured transitions. The results were analysed with three freely available computer programs employing different strategies for dealing with internal rotation and a comparative discussion of their merits is made.     

Internal rotation effects in the pulsed jet rotational spectrum of the trifluoromethane-carbon dioxide dimer

The rotational spectrum of the normal isotopic species of the HCF₃-CO₂ weakly bound complex has been measured by Fourier-transform microwave (FTMW) spectroscopy. All transitions are split into A and E states by internal rotation of the trifluoromethane subunit. A global fit of these states gives rotational constants that are consistent with a structure predicted by an MP2/6-311++G(2d,2p) ab initio calculation in which the axes of the monomers are coplanar, with the hydrogen atom of the trifluoromethane angled toward one of the oxygen atoms of the CO₂. Measured dipole moment components (μ_a = 0.431(6) D, μ_b = 0, μ_c = 1.436(6) D, μ_total = 1.499(6) D) confirm the ab initio prediction of an ac plane of symmetry; however, the very near-prolate nature of the complex (κ = −0.997), combined with the relatively high barrier to internal rotation (∼30 cm⁻¹) leads to asymmetry splittings and internal rotation splittings of similar magnitude, resulting in the observation of dipole forbidden b-type E-state transitions in addition to the expected a- and c-type lines. Although this effect has been observed previously in several monomer spectra, this appears to be one of few examples for a weakly bound complex.     

Rotational spectrum and structure of asymmetric dinitrogen trioxide, N2O3

The rotational spectra of the ground vibrational state and the ν₉ = 1 torsional state have been reinvestigated and accurate spectroscopic constants have been determined. The torsional frequency, ν₉ = 70(15) cm⁻¹, has been determined by relative intensity measurements. The assignment of the infrared spectrum has been slightly revised and an accurate harmonic force field has been calculated. The equilibrium structure has been determined using different, complementary methods: experimental, semi-experimental and ab initio, leading to r(NN) = 1.870(2) Å, in particular.     

FTMW spectroscopy of jet-cooled 9-cyanoanthracene

Rotational spectrum of jet-cooled 9-cyanoanthracene has been observed in the 4-8 GHz region with a Fourier-transform microwave spectrometer. The present observation of 25 low-J transitions with J^′′?11 has confirmed the previous results on the rotational constants of the ground state determined by rotational coherence spectroscopy [J. Phys. Chem. A. 105 (2001) 1131] and provided the values with significantly improved precision. An accurate set of hyperfine splitting constants is also reported for the ¹⁴N nuclear quadrupole coupling. The electric dipole moment was determined from Stark effect measurements on several split components: μ_b(=μ)=4.406(7) D.     

The high-resolution FTIR spectrum of the ν6 band of C2H3D

The absorption spectrum of the ν₆ band of C₂H₃D centered near 1125.27674 cm⁻¹ in the 1100-1250 cm⁻¹ region was recorded with an unapodized resolution of 0.0063 cm⁻¹ using a Fourier transform infrared (FTIR) spectrometer. A total of 947 infrared transitions of the A-B hybrid-type band were assigned and fitted to upper-state (ν₆ = 1) rovibrational constants using a Watson’s A-reduced Hamiltonian in the I^r representation up to eighth-order centrifugal distortion terms. The b-type infrared transitions of the band were analyzed for the first time. The root-mean-square deviation of the fit was 0.00062 cm⁻¹. The ground-state rovibrational constants up to eighth-order terms were also obtained by a fit of 617 combination differences from the present infrared measurements, simultaneously with 21 microwave frequencies with a root-mean-square deviation of 0.00055 cm⁻¹. From this work, the upper-state (ν₆ = 1) and ground-state constants of C₂H₃D were derived with the highest accuracy, so far. The a- and b-type transitions of the hybrid ν₆ band were found to be relatively free from local frequency perturbations. The ratio of the a- to b-type vibrational dipole transition moments (μ_a/μ_b) was found to be 1.05 ± 0.10. From the ν₆ = 1 rovibrational constants obtained, the inertial defect Δ₆ was calculated to be 0.3570 ± 0.0008 μŲ.     

New assignments, line intensities, and HITRAN database for CH3OH at 10 μm

The Fourier transform spectrum of CH₃OH in the 10 μm region has been re-examined at higher pressure and path length than heretofore, as part of a program to provide comprehensive CH₃OH spectral data for astrophysical and atmospheric applications. With the increase in spectral sensitivity, it has been possible to assign new torsionally excited ν₁₂=1 and ν₁₂=2 subbands plus further high-K, ν₁₂=0 subbands of the ν₈ CO-stretching band. Upper-state term values have been determined, and have been fitted to J(J+1) power-series expansions in order to obtain the excited ν₈ substate origins. A variety of weaker subbands from other modes has also been identified in the 10 μm spectrum including ν₁₂=0, ν₁₂=1, and ν₁₂=0←1 torsional subbands of the ν₇ in-plane CH₃ rock, ν₁₂=0←1 and ν₁₂=0←2 torsional combination subbands of the ν₆ OH bend, and ν₁₂=0←2 subbands of the ν₅ symmetric CH₃ bend. Line intensities have been retrieved line-by-line from the spectra. A large set of “unperturbed” ν₈ transitions has been modeled using the same type of multi-parameter effective Hamiltonian employed successfully for the ground state, with inclusion of the intensities of a subset of the stronger ν₈ spectral lines in the fitting in order to obtain appropriate transition dipole terms. Together, a 10 μm methanol database in HITRAN format has been generated.     

Sub-millimeter wave spectroscopy of the C3H radical: Ro-vibrational transitions from ground to the lowest bending state

Linear C₃H in its (X²Π) electronic ground state possesses strong Renner-Teller coupling in the two lowest bending modes, ν₄ and ν₅. The ²Σ^μ level of the v₄ = 1 bending mode is shifted towards lower energies and is supposed to lie only 20.3 cm⁻¹ above the ground state [S. Yamamoto, S. Saito, H. Suzuki, S. Deguchi, N. Kaifu, S. Ishikawa, M. Ohishi, Astrophys. J. 348 (1990) 363]. In the present study, first measurements of ro-vibrational transitions from the ²Π_3/2 ground state to the ²Σ^μ lowest vibrational state were performed using a Terahertz spectrometer equipped with a supersonic jet nozzle. Rotational levels of the ²Π_3/2 and v₄ = 1(²Σ^μ) state are close in energy and a crossing of the rotational energy ladders occurs between J = 24.5 and 25.5. A strong vibronic coupling leads to a significant intensity enhancement of ²Π_3/2 − ²Σ^μ ro-vibrational transitions. The search for ro-vibrational transitions was facilitated by measurements on pure rotational transitions in the ²Π_1/2, ²Π_3/2 and v₄ = 1(²Σ^μ) states, substantially extending the former data set published by Yamamoto et al. Data analysis yields an accurate value for the v₄ = 1(²Σ^μ) energy level which has been found to lie 609.9771(42) GHz or 20.34664(14) cm⁻¹ above the ²Π ground state. Furthermore, the value of the vibronic coupling constant β has been improved significantly and determined as 1231.77(51) MHz. The new set of spectroscopic parameters obtained in the present study permits very reliable frequency predictions into the Terahertz region.     

Millimeter wavelength measurements of the rotational spectrum of 2-aminoethanol

Aminoethanol is a predicted precursor to the amino acid alanine in the interstellar medium and is therefore of great interest for observational studies. However, previous work involving the rotational spectrum of this molecule is limited to centimeter wavelengths and additional laboratory work is necessary to support astronomical heterodyne spectroscopy. This work presents the Doppler-limited rotational spectrum of aminoethanol measured in selected regions between 72 and 305 GHz. Measurements of ground state and ν₂₇ transitions have been extended up to J=51 and J=43, respectively. Additional rotational transitions were assigned for the ν₂₅, ν₂₆, ν₂₅+ν₂₇, 2ν₂₇ and ν₂₆+ν₂₇ hot bands, resulting in improved rotational and centrifugal distortion constants for these states.     

A new joint analysis of the ground and first excited torsional states of methylformate

A global fit within experimental accuracy of microwave rotational transitions in the ground and first excited torsional states (v_t = 0 and 1) of methylformate (HCOOCH₃) is reported, which combines older measurements from the literature with new measurements from Kharkov. In this study the so-called ‘‘rho axis method’’ that treats simultaneously both A and E species of the ground and first excited torsional states is used. The final fit requires 55 parameters to achieve an overall unitless weighted standard deviation of 0.71 for a total of 10533 transitions (corresponding to 9298 measured lines) with rotational quantum numbers up to J ? 62 and K_a ? 26 in the ground state and J ? 35 and K_a ? 23 in the first excited torsional state. These results represent a significant improvement over past fitting attempts, providing for the first time a fit within experimental accuracy of both ground and first excited torsional states.     

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.     

Interactions between vibrational polyads of propyne, H3CCCH: Rotational and rovibrational spectroscopy of the levels around 1000 cm

The study of vibration resonance physics in propyne is based on experimental measurements of about 600 new rotational transitions between 495-590 and 700-760 GHz in excited vibrational levels v₅ = 1, v₈ = 1, v₁₀ = 3 and v₉ = v₁₀ = 1 with vibrational energies around 1000 cm⁻¹. The limits to the assignments and analysis were imposed by as yet unresolved anharmonic resonances with the states of the next higher polyad of levels lying above 1200 cm⁻¹, which affect the rotational states involved in transitions that would be measurable with non-vanishing intensities. Vibration-rotation spectra pertaining to the levels in question were studied in the regions 880-1150 cm⁻¹ (the ν₅ and ν₈ fundamental bands), 550-750 cm⁻¹ (the v₉ = v₁₀ = 1 ← v₁₀ = 1 hot bands) and 250-400 cm⁻¹ (the v₁₀ = 3 ← v₁₀ = 2 “superhot” bands). A simultaneous least-squares fit of both types of data provides their reliable but in the case of accurate rotational data not always fully quantitative reproduction.     

High resolution infrared spectrum and global analysis of ν5, ν12, and ν12 + ν6 − ν6 in CH3SiH3

The vibration-torsion-rotation spectrum of CH₃SiH₃ has been measured from 470 to 725 cm⁻¹ at near-Doppler resolution. The full-width at half - maximum of the lines observed near 600 cm⁻¹ was 0.0011 cm⁻¹. The spectra were obtained using a Bruker IFS 125 HR Fourier transform spectrometer with the broadband source radiation being supplied from the synchrotron emission of the storage ring at the Canadian Light Source. Three vibrational bands were investigated: the lowest lying perpendicular fundamental ν₁₂ centred near 524 cm⁻¹, the lowest lying parallel fundamental ν₅ near 703 cm⁻¹, and the torsional hot band ν₁₂ + ν₆ − ν₆ near 534 cm⁻¹. For ν₁₂ and ν₅, the resolution and sensitivity are much improved over those in earlier studies, with many of the torsional multiplets now being resolved even in the cases where the upper levels are unperturbed. The primary motivation for the present work was the hot band, here reported for the first time, where the dependence of the silyl rock in ν₁₂ on the torsional motion is much more pronounced. In addition, for the vibrational ground state (gs), two “forbidden” high torsional overtones v₆ = 3 ← 0 and 5 ← 0 have been observed that become allowed through resonant mixing of the upper states with ν₁₂ and ν₅, respectively. In each case, two (K, σ) series have been measured where the mixing is largest. Here σ = 0, 1, −1 labels the torsional sub-levels. Using the Fourier transform waveguide spectrometer at E. T. H., the three σ-components of the (J = 1 ← 0) transition in ν₁₂ + ν₆ were observed, and a series of direct l-doubling transitions in ν₁₂ + ν₆ were measured for σ = 0. In a global fit, all the new data have been analysed along with the frequencies for other transitions obtained in earlier investigations. The analysis takes into account the relevant interactions among the torsional stacks of levels in the gs, ν₁₂, and ν₅. These include the previously known (gs, ν₁₂) Coriolis-like and (gs, ν₅) Fermi-like interactions along with a higher order (ν₁₂, ν₅) Coriolis-like coupling introduced here. This last is responsible for the strong perturbation of the ν₅ series with K = 10, 11, and 12, and of the corresponding hot band series. A good fit to 9282 frequencies including 7942 new measurements was obtained both with the Free Rotor model in which the torsion is classified as a rotation, and with the High Barrier model in which the torsion is classified as a vibration. The Hamiltonian is discussed with emphasis on the new terms required for treating ν₁₂ + ν₆ − ν₆.     

The Rotational Spectrum of SiHF3 in the Vibrational State υ6=2: Observation of Direct l-Type Resonance Transitions

The υ₆=2 vibrational state of the main isotopomer of trifluorosilane, ²⁸SiHF₃, has been investigated in the centimeter- and millimeter-wave ranges. Rotational spectra following the Δ J=1, Δk=Δ l=0 selection rule have been measured up to J=24 and K=23 and for both values of ∣l∣. Two types of direct l-type resonance transitions induced by the (Δ l=Δk=±2) interaction could be observed by means of waveguide Fourier transform microwave spectroscopy in the range 8-26 GHz: 252 transitions following the Δ J=0, Δl=Δk=±2 selection rule covering values of J=7-39 and G=∣k-l∣ from 1 to 18 and 90 transitions following the Δ J=0, Δl=Δ k=±4 selection rule covering values of J=17-52 and G from 1 to 4. Due to the strong (2,2) resonance, 18 A₁-A₂ splittings of the k=l=±2 states from J=36-53 could also be observed. Accidental near-degeneracies lead to strong perturbations due to Δ (k-l)=±3 interactions, enabling the observation of perturbation-allowed transitions with selection rules k=±3(l=±2)↔±4(±2), ±2(±2), A₊↔ ±1(?2), A₋ and ± 1(0)↔± 6(±2). In a multiple-fit analysis the experimental data have been refined using five reduced forms of the effective Hamiltonian as proposed by Sarka and Harder [J. Mol. Spectrosc.197, 254-261 (1999)]. Parameters up to seventh order have been determined including the axial rotational constant C for both values of ∣l∣ and the vibrational separation of the ∣l∣=0 and 2 states. The unitary equivalence of the determined parameter sets has been demonstrated up to fifth order. Differences of the rotational constants in the various parameter sets have been explained by the theory of reduction. Sign relations of the fitted parameters and general features of the direct l-type resonance spectrum in a υ_t=2 level are discussed.     

A new analysis of the ν4(E) rovibrational band of the symmetric top molecule PF3

The high-resolution Fourier transform infrared spectrum of phosphorus trifluoride PF₃ have been reinvestigated in the ν₄ perpendicular band region around 347 cm⁻¹. Thanks to recent pure rotational measurements, 595 new infrared transitions of the ν₄ band have been assigned extending the rotational quantum number values up to K_max = 66 and J_max = 67. As a consequence of this extension, a sophisticated model containing a large number of parameters and interaction constants was adopted for the analysis of the IR transitions of the ν₄ fundamental band of PF₃. A merge of the IR transitions and the reported MW/MM/RF data within the v₄ = 1 excited level yielded an accurate rotational ground state C₀ value, 0.159970436 (69) cm⁻¹, which was used to determine an improved GS structure, r₀(P-F) = 1.56324405 (11) Å and ?(FPF) = 97.752232 (29)°. All experimental data have been refined applying various reduction forms of the effective rovibrational Hamiltonian developed for an isolated degenerate state of a symmetric top molecule. The v₄ = 1 excited state of the PF₃ oblate molecule was treated with models taking into account ?- and k-type intravibrational resonances. Parameters up to sixth order have been accurately determined and the unitary equivalence of the derived parameter sets in different reductions was demonstrated.     

Measurements of NH3 in the ν2 = 1 state by a solid-state, photomixing, THz spectrometer, and a simultaneous analysis of the microwave, terahertz, and infrared transitions between the ground and ν2 inversion-rotation levels

In this paper, we report 30 THz measurements of ammonia in its excited, ν₂ = 1, inversion state. These measurements include transition frequencies and pressure shifts (where significant enough to be observed). Included in the data are two forbidden and three ro-inversion transitions, as well as 18 transitions never directly measured before. The measurements were made with an all-solid-state, diode-laser, difference-frequency spectrometer. Using an innovative laser-frequency locking scheme, this spectrometer provided accurately determined and continuously tuned THz-frequencies without requiring accurate knowledge of the absolute laser frequencies. The details of the spectrometer’s frequency calibration is discussed. A global analysis of NH₃ based on the available ground state, ν₂ = 1 state, and ν₂-band transitions was carried out, and the resulting set of recommended molecular effective-Hamiltonian parameters for ammonia is presented. In addition, calculated center frequencies and intensities for all possible transitions up to J = 20 between rotation, inversion, and vibration levels in the ground and ν₂ = 1 states are included as supplementary material.