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.     

Room temperature chirped-pulse Fourier transform microwave spectroscopy of anisole

The room-temperature rotational spectrum of anisole from 8.7 to 18.3 GHz was collected with a waveguide-based chirped-pulse Fourier transform microwave spectrometer whose operating principles are described. Three spectra were assigned, corresponding to the vibrational ground state and the first and second excited states of the lowest frequency torsional mode. Results for the ground state and first excited state are in agreement with prior millimeter wave studies of this molecule. Microwave–microwave double resonance measurements also confirm these assignments.     

Microwave spectrum of chloromethyl methyl ether

The microwave spectrum of chloromethyl methyl ether has been studied in the region 12.4–40 GHz. For ³⁵Cl species, a- and c-type transitions have been assigned for the ground state, the first excited state of the chloromethyl torsional mode, and the first excited state of the methyl torsional mode. Assignments were also made for the ground state of ³⁷Cl species. The assigned transitions are due to the gauche conformer. The nuclear quadrupole coupling constants were determined for the ground state of ³⁵Cl and ³⁷Cl species. The observed A-E splittings of the rotational transitions arising from the three vibrational states indicate a strong coupling between the two torsional vibrations. A model calculation based on the Hamiltonian previously used by Butcher and Wilson (J. Chem. Phys.40, 1671 (1964)), was carried out to account for the splittings and the vibrational frequencies of the two torsional modes. The barrier to internal rotation of the methyl group is estimated to be V₃ = 647 ± 17 cm^?1 (1.84 ± 0.05 kcal/mole).     

Analysis of microwave and infrared transitions of phenol by rotation-internal rotation theory. Phenol-OD

Rotational transitions of the torsional ground and first excited state of phenol-OD have been measured in the frequency range 8–40 GHz. In a semi-rigid model approach to the internal rotation, kinetic and potential constants have been fitted to the far-infrared torsional frequencies and the microwave transition frequencies for the ground and the excited state separately. It is further shown that an acceptable agreement between observed and calculated spectra has simultaneously been obtained for the torsional ground and first excited state using the contravariant kinetic coefficients g^mn as fitting parameters.     

Global fit of rotational transitions of methyl formate (HCOOCH3) in the ground and first excited torsional states

The microwave spectrum of methyl formate (HCOOCH₃) has been observed in the frequency range from 7 to 200 GHz. New 348 lines were assigned to E-species in the first excited torsional state. By combining these lines with previously reported data, a global analysis of A- and E-species lines of the ground and first excited torsional states were carried out on the basis of the internal axis method. A total of 3862 transitions were fitted to a Hamiltonian model involving 69 molecular parameters to a weighted unitless standard deviation of 1.96.     

Internal rotation and inversion doubling in the microwave spectrum of CH3NHCl

The microwave “a” and “c” type spectra of four isotopic species of CH₃NHCl in the ground state and of CH₃NHCl³⁵ and CH₃NDCl³⁵ in the first excited torsional state have been analyzed. From the A-E torsional splittings of the excited state the torsional barrier height has been determined to be V₃ = 3710 ± 46 cal/mole. The “c” type transitions show an inversion doubling of 4.60 ± 0.10 MHz in the ground state and of 5.25 ± 0.10 MHz in the first excited torsional state. Such doublings are independent on the rotational quantum numbers within the experimental errors. The height of the inversion barrier has been roughly evaluated by using the Dennison-Uhlenbeck potential.     

The OH stretching fundamental of hydroxylamine

The OH stretching fundamental of hydroxylamine, ν₁, has been studied using a computer-controlled color center laser spectrometer. Absorption and Stark-modulated spectra of this AC hybrid band were obtained in the spectral region from 3630 to 3710 cm^?1. The spectrum is dominated by many strong perpendicular c-type Q branches, but both parallel and perpendicular type transitions are observed. The rotational structure has been fitted by least squares, and rotational and centrifugal distortion constants have been obtained for both states. The excited state exhibits many small perturbations. All lines observed are believed to originate from the trans form of hydroxylamine and no evidence for the cis isomer was found. Transitions belonging to a hot band, in which the low-energy torsional motion is excited in both the ground and upper states, have been located and assigned.     

Microwave spectrum of 3-bromopropene in the excited torsional states

The microwave spectra in the excited states of the CC torsion for the ⁷⁹Br and ⁸¹Br isotopic species of 3-bromopropene were measured in the frequency region 15.3–23.7 GHz. The a-type R-branch and b-type Q-branch rotational transitions in the first and second excited states of one conformer, skew, have been assigned and analyzed. Analysis of the spectrum yields the rotational constants and the nuclear quadrupole coupling constants. From relative intensity measurements the energy differences associated with the CC torsion, between the ground and first excited state, the ground and second excited state have been found to lie 109 and 206 cm^?1, respectively.     

Spectra and structure of small ring compounds. Microwave spectrum of cyanocyclobutane

The rotational spectrum of cyanocyclobutane has been investigated in the region 18.0–40.0 GHz. Only A-type transitions were observed. R-branch assignments have been made for the ground state and the first three excited states of the ring puckering mode as well as the first two excited states of the out-of-plane cyano-bending mode. The microwave data are consistent with a bent equilibrium ground state for the ring with the cyano-group in the equatorial position. The dipole moment components were determined to be μ_a = 4.04 ± 0.09 D and μ_c = 0.92 ± 0.03 D with the total dipole moment, μ, having a value of 4.14 ± 0.09 D.     

Microwave spectrum,dipole moment,and structure of 3-aminopropanol

The microwave spectra of 3-aminopropanol and three of its deuterium substituted isotopic species have been investigated in the 26.5 to 40 GHz frequency region. The rotational spectrum of only one conformer has been assigned in which presumably a hydrogen bond of the OH---N type exists. The rotational spectra of a number of excited vibrational states have been observed and assignments made for some of these excited states. The average intensity ratio for the rotational transitions between the ground and excited vibrational states indicates that the first excited state is about 120 cm^?1 above the ground state.and the next higher state is roughly 200 cm^?1 above the ground vibrational state. The dipole moment was determined from the Stark effect measurements to be 3.13 ± 0.04 D with its principal axes components as |μ_a| = 2.88 ± 0.03 D, |μ_b| = 1.23 ± 0.04 D and |μ_c| = 0.06 ± 0.01 D. The possibility of another conformer where the hydrogen bond could be of NH---O type was explored, but the spectra of such a conformer could not be identified.     

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.     

Microwave spectrum of CH3OD

The microwave spectrum of CH₃OD has been observed in the frequency region between 14 and 92 GHz. All the ground-state transitions with J ≤ 8 and J = 2 ← 1, a-type transitions in the excited torsional states (v = 1 and v = 2) have been observed. The spectrum has been analyzed and rotational constants, torsional constants, torsion-vibration-rotation interaction constants, and centrifugal distortion constants have been evaluated. The Stark effect measurements have been made and the dipole moment components have been determined as μ_a = 0.833 ± 0.008 D and μ_b = 1.488 ± 0.015 D.     

Conformation of 4-methylcyclohexanone by microwave spectroscopy

The microwave spectrum of 4-methylcyclohexanone has been observed in the frequency region from 18.0 to 26.5 GHz. Both a-type and c-type transitions in the ground state and a-type transitions in four excited states have been assigned. The ground state rotational constants are determined to be A = 4034.39 ± 0.06 MHz, B = 1455.46 ± 0.01 MHz, and C = 1174.06 ± 0.01 MHz. From these data, it is shown that the most stable conformer exists in the chair form with the methyl group in the equatorial position.     

Determination of the Dipole Moment of O-18 Methanol by Microwave Stark Spectroscopy

In this paper we report accurate measurements of microwave (MW) frequencies for nine different transitions in the first four torsional states in the ground vibrational state of O-18 substituted methanol, for a wide range of applied dc electric field. The Stark-shifted frequencies were measured with accuracies of about ±10 kHz. The results were analyzed to deduce accurate dipole moment values for the four torsional states involved. Substantial variation of dipole moment was observed as a function of the torsional state. The zero field frequencies have been also determined with much better precision than known before. The dipole moment values for the torsional ground state have been determined to be μ_a= 0.8992(8) and μ_b= 1.4226(3) D. The dipole moment value increases with torsional excitation. These values will be useful for the evaluation of relative intensities of interstellar microwave and millimeter wave transitions and optically pumped far infrared laser lines.     

Conformation and dipole moment of tetrahydropyran-4-one by microwave spectroscopy

The microwave spectrum of tetrahydropyran-4-one has been studied in the frequency region 18 to 40 GHz. The rotational constants for the ground state and nine vibrationally excited states have been derived by fitting a-type R-branch transitions. The rotational constants for the ground state are (in MHz) A = 4566.882 ± 0.033, B = 2538.316 ± 0.003, C = 1805.878 ± 0.004. From information obtained from the gas-phase far-infrared spectrum and relative intensity measurements, these excited states are estimated to be ～ 100 cm^?1 above the ground state for the first excited state of the ring-bending and ～ 185 cm^?1 for the first excited state of the ring-twisting mode. Stark displacement measurements were made for several transitions and the dipole moment components determined by least-squares fitting of the displacements: (in Debye) |μ_a| = 1.693 (0.001), |μ_b| = 0.0, |μ_c| = 0.300 (0.013) yielding a total dipole moment μ_tot = 1.720 (0.003). A model calculation to reproduce the rotational parameters indicates that the data are consistent with the chair conformation.     

Microwave spectra of thionyl fluoride in vibrationally excited states

The microwave spectrum has been observed and rotational constants obtained for the v₄ = 1 and v₆ = 1 vibrationally excited states of thionyl fluoride. The perturbation of the C rotational constant is explained in terms of a Coriolis resonance between these levels.     

The millimeter-wave spectrum of perdeuterated methanol, CD3OD

In order to provide accurate rest frequencies for astronomical searches, the spectrum of perdeuterated methanol, CD₃OD, has been measured in the frequency range 62-233 GHz. A total of 379 lines was measured from rotational states up to J=20 and K=10 within the ground and first excited torsional states (v_t=0 and 1). Using a one-dimensional torsion-rotation Hamiltonian, the lines were fitted to measurement accuracy (<30 kHz).     

Microwave spectra of deuterated ethanes: Internal rotation potential function and rz structure

The microwave spectra of CH₃CHD₂ in the first excited torsional state and of CH₃CH₂D and CD₃CH₂D in the ground states have been observed by a source-modulation spectrometer and analyzed to determine the two potential constants, V₃ and V₆, simultaneously and also to assess the isotopic effects on the potential function. The results obtained for C₂H₆ are V₃ = 2.882 ± 0.010 and V₆ = 0.020 ± 0.010 kcal/mole. The staggered conformation in ethane was established by observing microwave spectra of gauche CH₂DCH₂D. The r_z structure of ethane was recalculated by adding precise rotational constants obtained in this work to previous microwave and infrared data.     

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.     

Spectroscopic constants of the ground and lower vibrational states of CH2BrF: A combined high resolution infrared and microwave study

The enriched ⁸¹Br isotopic species of bromofluoromethane has been investigated in the infrared and microwave regions. The rovibrational spectrum of the ν₅ fundamental has been studied by high resolution FTIR spectroscopy, while the rotational spectra of the ground and v₆ = 1 states have been observed by means of microwave spectroscopy. More than 2700 transitions have been assigned in the ν₅ band and the analysis of the rovibrational structure reveals a first-order c-type Coriolis resonance with the v₆ = 2 state. The present study improves the ground state constants available in the literature and enables the determination of further centrifugal distortion parameters together with the full bromine quadrupole coupling tensor. A set of spectroscopic parameters up to the sextic distortion terms for the vibrational excited states has been accurately evaluated for the first time.