The rotational spectrum of acetone: Internal rotation and centrifugal distortion analysis

In the rotational spectrum of acetone, 52 new quartets (up to 300 GHz, J≤30) have been measured. Because the barrier hindering internal rotation is low (s = 21), a new computer program based on the Internal Axis Method has been developed. It has allowed us to satisfactorily fit the spectrum and to accurately determine the rotational constants, centrifugal distortion constants, and the three internal rotation parameters.     

Centrifugal distortion analysis of the rotational spectrum of aziridine: Comparison of different Hamiltonians

Previous measurements of rotational spectrum of aziridine up to 1.85 THz have been supplemented by new data in 225-660 GHz frequency range. A total of 1465 transitions (915 of them are newly assigned ones) with maximum values of J = 59 and K_c = 50 were fit to a standard Watson Hamiltonian using the S- and A-reductions and the representations I^r and III^r. Although aziridine is an asymmetric oblate top, the combination (A, III^r) gives the worst results. From the point of view of the convergence of the Hamiltonian, the best results are obtained with the combination (S, III^r). It is explained that the failure of the combination (A, III^r) is due to the large value of the parameter σ=(2C-A-B)/(A-B) which makes some sextic centrifugal distortion constants much too large impeding the convergence of the Hamiltonian. It is also shown that the calculation of the centrifugal distortion constants from a force field is sometimes an ill-conditioned operation. Finally, the use of a non-reduced Hamiltonian (with six quartic centrifugal distortion constants) was successful in the particular case thanks to the method of predicate observations.     

Microwave spectrum of dimethylallene : Centrifugal distortion analysis

The rotational absorption lines of the molecule dimethylallene in the vibrational ground state deviate from a rigid rotor pattern by shifts due to centrifugal distortion and by shifts and splittings due to methyl top internal rotation. By enlarging the number of previously measured lines it has been possible to apply successfully a Watson-type centrifugal distortion formula and to analyze the resulting “effective rigid rotor” rotational constants for the remaining contributions due to internal rotation and centrifugal distortion. Care has been taken to calculate or at least estimate the separate contributions and compare their magnitudes.     

Centrifugal distortion constants of pentafluorobenzene from its pure rotation spectrum

The centrifugal distortion analysis of the pure rotational spectrum of pentafluorobenzene in the frequency region of 8 to 18 GHz involvingJ upto 54 has yielded the following rotational and quartic centrifugal distortion constants: $$\begin{gathered} A'' = 1480 \cdot 8665 \pm 0 \cdot 0026 MHz, \tau = - 1 \cdot 751 \pm 0 \cdot 20 kHz, \hfill \\ B'' = 1030 \cdot 0782 \pm 0 \cdot 0025 MHz, \tau _2 = - 0 \cdot 567 \pm 0 \cdot 066 kHz, \hfill \\ C'' = 607 \cdot 5152 \pm 0 \cdot 0026 MHz, \tau _{aaaa} = - 0 \cdot 765 \pm 0 \cdot 068 kHz, \hfill \\ \tau _{bbbb} = - 0 \cdot 612 \pm 0 \cdot 065 kHz, \hfill \\ \tau _{cccc} = - 0 \cdot 547 \pm 0 \cdot 068 kHz. \hfill \\ \end{gathered} $$      

Millimeterwave rotational spectrum and internal rotation in o-chlorotoluene

The millimeterwave rotational spectrum of o-chlorotoluene is investigated in the frequency region 150-250 GHz. Many rotational lines show splitting due to internal rotation of the methyl group. The analysis of the internal rotation splitting allows us to determine with precision the potential barrier to internal rotation of the methyl group. However, it is found that the moment of inertia of the methyl top is probably much smaller than usually assumed, which significantly affects the value of the barrier. Accurate centrifugal distortion constants are obtained for the ground states of ³⁵Cl and ³⁷Cl isotopologues as well as for an excited vibrational state.     

Centrifugal distortion and internal rotation analysis of the rotational spectra of N-methylmethanimine d0 and d5

The ground state millimeter-wave spectra of CH₃NCH₂ and CD₃NCD₂ have been measured. The rotational constants, centrifugal distortion constants, and barrier hindering internal rotation of the methyl group have been determined for both species. For the parent species I_α and ?(i,a) were also obtained, and for the perdeuteriated species the quadrupole coupling constants of ¹⁴N were determined.     

Microwave spectrum of dimethylketene: Centrifugal distortion and Coriolis interaction

For the prolate asymmetric (κ = ?0.58) top molecule dimethylketene the centrifugal constants have been determined in terms of the Δ constants by means of ΔK_? ≠ 0 rotational transitions. Two earlier assigned torsional excited states (01, 10)₁ and (01, 10)₂ of symmetry B₂ and A₂ of C_2v could be confirmed. A third fundamental vibration v_r(b₁), probably the inplane skeletal rock, has been found and analyzed in the v_r = 1 and v_r = 2 states. The variation of the centrifugal constants and of the inertial defects with the state of excitation could be explained by Coriolis coupling between the v_r(b₁) = 1 vibrational and v_t(b₂) = 1 torsional excited states. The Coriolis constant $\text{ζ}{}_{\mathrm{rt}}{}^{\mathrm{a}}$ and the torsional frequency ω_t(b₂) have been estimated to be $\text{ζ}{}_{\mathrm{rt}}{}^{\mathrm{a}}\text{≈ 0.24}$ and ω_r(b₁) - ω_t(b₂) ≈ 5.8 cm^?1, respectively.     

Centrifugal distortion analysis of difluoramine

The microwave rotational spectrum of difluoramine (NF₂H) has been analyzed in the frequency region 15–36 GHz involving rotational levels up to J = 19. The analysis gives refined rotational constants and all quartic centrifugal distortion constants. These constants have been used to predict additional Q-branch transitions of the molecule in the frequency region 5–95 GHz.     

Centrifugal distortion constants of the NGLT form of allylamine from microwave spectrum analysis

The centrifugal distortion analysis of the microwave spectrum of the N-gauche lone-electron-pair trans (NGLT) rotameric form of allylamine has been carried out in the frequency region 5–40 GHz and up to J = 29 in its ground vibrational state. The analysis gives effective rotational constants and all the quartic centrifugal distortion constants.     

Centrifugal distortion effects in the hyperfine spectrum of KCl

The hyperfine spectrum of KCl has been examined at near-zero electric field and zero magnetic field using a molecular beam electric resonance spectrometer. Rotational as well as vibrational shifts have been observed in both nuclear quadrupole interactions. With $\text{eqQ = Q}{}_{00}\text{+ Q}{}_{10}\text{(v +}\text{1}\text{2}\text{) + Q}{}_{20}\text{(v +}\text{1}\text{2}\text{)}{}^2\text{+ Q}{}_{01}\text{J(J + 1)}$, we find (all in units of kHz) for K in ³⁹K³⁵Cl: Q₀₀ = ?5691.47 ± 0.04, Q₁₀ = 51.32 ± 0.06, Q₂₀ = ?0.205 ± 0.020, Q₀₁ = 0.014 ± 0.007, Q₀₀(K³⁷Cl) ? Q₀₀(K³⁵Cl) = ?0.03 ± 0.07; for Cl in ³⁹K³⁵Cl: Q₀₀ = 137.0 ± 0.3, Q₁₀ = ?163.2 ± 0.5, Q₂₀ = 1.57 ± 0.15, Q₀₁ = 0.07 ± 0.03, $\text{[}\text{Q(}{}^{35}\text{Cl}\text{)}\text{Q(}{}^{37}\text{Cl}\text{)}\text{]Q}{}_{00}\text{(}\text{K}{}^{37}\text{Cl}\text{) ? Q}{}_{00}\text{(}\text{K}{}^{35}\text{Cl}\text{) = ?0.5 ± 0.6}$; and magnetic constants c_K = 0.154 ± 0.007, c_Cl = 0.435 ± 0.010, c₃ = 0.035 ± 0.012, and c₄ = 0.009 ± 0.006. These have been used to provide a mapping of the field gradients at both nuclear sites to fourth order in $\text{ξ =}\text{(r ? r}{}_{\mathrm{e}}\text{)}\text{r}{}_{\mathrm{e}}$. We find eQq_K(ξ) = (?5692.5 ± 2.5) + (1.7 ± 0.8) × 10⁴ξ + (?2. ± 4.) × 10⁴ξ² + (?8. ± 18.) × 10⁵ξ³ + (8. ± 15.) × 10⁶ξ⁴ and eQq_Cl(ξ) = (120. ± 22.) + (8. ± 4.) × 10⁴ξ + (?5.8 ± 2.0) × 10⁵ξ² + (?1.1 ± 1.6) × 10⁷ξ³ + (1.1 ± 1.3) × 10⁸ξ⁴.     

Centrifugal distortion analysis of the millimeter-wave spectrum of 2-fluorobenzonitrile and ab initio DFT calculations

The ground state (ν = 0) rotational spectrum of 2-fluorobenzonitrile has been reinvestigated in the frequency range 40.0-99.0 GHz. The millimeter-wave spectrometer used is a source-modulated system combined with a free space glass cell. Millimeter-wave radiation has been produced using a Gunn diode and frequency doubler combination. High J and K₋₁ (J ? 49 and K₋₁ ? 18) transitions have been measured and accurate rotational and centrifugal distortion constants have been determined. Finally, the experimental values were compared with the corresponding values calculated at the HF/DFT-B3PW91/6-31g(d,p) level of theory. A very good agreement has been found.     

Centrifugal distortion analysis of the microwave spectrum of allyl isothiocyanate (C-gauche conformer)

The ground state microwave rotational spectrum of the C-gauche conformer of allyl isothiocyanate has been reinvestigated by extending the frequency range up to 37.0 GHz. A detailed centrifugal distortion analysis has been carried out with previously reported and newly assigned microwave rotational transition frequencies. The evaluated rotational and centrifugal distortion constants are presented.     

Centrifugal distortion effects in the microwave spectrum of allyl alcohol

The ground state rotational spectrum of allyl alcohol has been reinvestigated in the frequency range 12.5–40.0 GHz. A detailed centrifugal distortion analysis has been carried out and theJ-value of the assigned transitions has been extended to 45. The evaluated parametes are presented.     

Centrifugal distortion effects in the microwave spectrum of methylene cyanide

The rotational spectrum of methylene cyanide has been measured up to J = 62 and a total of 82 b-type transitions have been obtained. These data have been analyzed with a semirigid rotor Hamiltonian to give accurate rotational and centrifugal distortion constants. The rotational constants are (in MHz) $\text{A}$ = 20882.7537 ≠ 0.017, $\text{B}$ = 2942.3003. ≠ 0.0031, $\text{C}$ = 2616.7225 ≠ 0.0031 The quartic centrifugal distortion constants are (in MHz)

$\text{Δ}{}_{\mathrm{J}}\text{(1.855455 ≠ 0.014) x 10}{}^{\mathrm{?3}}\text{Δ}{}_{\mathrm{JK}}\text{= (?6.79218 ≠ 0.027) x 10}{}^{\mathrm{?2}}$

$\text{Δ}{}_{\mathrm{K}}\text{(8.621628 ≠ 0.013) x 10}{}^{\mathrm{?1}}\text{δ}{}_{\mathrm{J}}\text{= (4.892607 ≠ 0.016) x 10}{}^{\mathrm{?4}}$

$\text{δ}{}_{\mathrm{K}}\text{= (6.7501 ≠ 0.29) x 10}{}^{\mathrm{?3}}$

The uncertainties are twice the standard deviations in the constants obtained from the least squares analysis, and represent approximately 95% confidence limits.     

Centrifugal distortion coefficients of asymmetric-top molecules: Reduction of the octic terms of the rotational Hamiltonian

The rotational Hamiltonian of an asymmetric-top molecule in its standard form, containing terms up to eighth degree in the components of the total angular momentum, is transformed by a unitary transformation with parameters S_pqr to a reduced Hamiltonian so as to avoid the indeterminacies inherent in fitting the complete Hamiltonian to observed energy levels. Expressions are given for the nine determinable combinations of octic constants Θ′_i (i = 1 to 9) which are invariant under the unitary transformation. A method of reduction suitable for energy calculations by matrix diagonalization is considered. The relations between the coefficients of the transformed Hamiltonian, for suitable choice of the parameters S_pqr, and those of the reduced Hamiltonian are given. This enables the determination of the nine octic constants Θ′_i in terms of the experimental constants.     

Microwave spectrum and selenol internal rotation of 2-propaneselenol

Microwave spectra of 2-propaneselenol and its deuterated species were measured and assigned for the gauche and trans isomers. The double minimum splittings of the gauche isomers were directly observed from b-type transitions, which were assigned with the aid of a double resonance technique. Rotational constants and torsional splitting of the gauche isomer of the parent species were determined to be A = 7802.50 ± 0.75, B = 2847.68 ± 0.04, C = 2242.03 ± 0.03, ΔA = ?2.52 ± 0.74, ΔB = 0.02 ± 0.05, ΔC = ?0.34 ± 0.03, and Δν = 368.91 ± 0.94 MHz, where ΔA, and ΔB, and ΔC are the differences of the rotational constants between the (+) and (?) states. From the torsional splittings and the energy differences of the two isomers of the parent and SeD species, Fourier coefficients of the selenol internal rotation potential function were determined to be V₂ = ?88 ± 15, V₃ = 1543 ± 29 cal/mole on the assumption of V₁ = 0. Dipole moments and their components were also obtained for the two isomers.     

Far-infrared spectrum of the internal rotation in methylamine

The far-infrared spectra of the Q branches of hindered rotation of CH₃NH₂ were studied in the 80 to 280 cm^?1 spectral region with resolutions up to 0.12 cm^?1. Through the theoretical analysis 11 of the 12 b-type parameters I_a1, I_a2, V₃, V₆, k₁, k₂, k₃, k₄, k₅, k₆, k₇, D_KK are determined using a nonlinear least-squares fit. The agreement between the observed and the final theoretical spectrum is satisfactory considering that only Q-branch lines were studied. Experimentally more lines, especially at low frequencies, were observed which probably belong to P- and R-branch lines of clusters thereof.     

Inversion and internal rotation in methyl-d-amine: Microwave spectrum

The microwave spectrum of CH₂DNH₂ has been observed in the 8–74 GHz region. The spectrum shows that this molecule takes essentially two distinguishable conformers, trans and gauche forms, although a small amount of coupling between them can be detected. For each line of the trans form a small inversion splitting has been found. It is 93.97 MHz at K = 0 and a periodic function of K. The mean frequencies of the inversion pairs of lines are well explained as the frequencies of a rigid rotor. The gauche spectrum is extremely complicated; each rotational line splits into four because of inversion and gauche-gauche tunneling interactions. The analysis was carried out based on the theory developed in the preceding paper. Tunneling energy parameters of internal-rotation, ?_gg and ?_tg, and inversion, δ_gg and δ_tg, were determined as ?_gg = 3476.6 MHz, ?_tg = 3233.1 MHz, δ_gg = 2790.6 MHz and δ_tg = 3052.7 MHz. Energy difference between trans and gauche conformers ΔE_tg was estimated to be 7.060 cm^?1 from these values of parameters and also on the basis of the observed anomaly in the Q branch series of trans form which is due to an accidental degeneracy between the K = 1 level of trans and K = 2 level of gauche. The effects on the internal-rotation of other internal motions have also been discussed.     

The microwave spectrum of methyl chlorodifluoroacetate: Methyl internal rotation and chlorine nuclear electric quadrupole coupling

A chirped pulse microwave spectrometer has been used to record microwave spectra of the ³⁵Cl and ³⁷Cl isotopologues of methyl chlorodifluoroacetate, CClF₂C(O)OCH₃, between 8 GHz and 16 GHz. The target compound was spectroscopically examined as it participated in a supersonic expansion of argon. Only one conformer was observed. The rotational spectra were recorded with sufficient resolution to observe (i) splittings due to the internal rotation of the methyl group, and (ii) splittings from the coupling of the chlorine quadrupolar nucleus. A total of 785 transitions have had quantum numbers assigned. Analysis of the spectra observed has produced an experimental barrier to the methyl group internal rotation, V₃, of 370(2) cm⁻¹. It is noted that this barrier is a little lower than that determined for methyl acetate [V₃ = 425 cm⁻¹, J. Sheridan, W. Bossert and A. Bauder, J. Mol. Spectrosc., 80 (1980) 1-11], and this is rationalized through a comparison of molecular structures. Lastly, all components of both the ³⁵Cl and ³⁷Cl chlorine nuclear electric quadrupolar coupling tensor have been determined.     

The rotational spectrum of silacyclohexane

The rotational spectra of the normal and Si-d₂ isotopomers of the chair form of silacyclohexane have been measured by microwave absorption spectroscopy. A partial r₀ structure has been obtained. The rotational spectra of some, the most intense, vibrational satellites have also been measured. They belong to the ring-puckering motions. Their vibrational energies and their shifts of planar moments of inertia with respect to the ground state indicate that the amplitude of these vibrations is larger than in cyclohexane. The dipole moment has also been determined: μ_a = 0.75(2), μ_c = 0.280(2), and μ_tot = 0.80(2) D.