Microwave spectrum and barrier to internal rotation of 1-chloro-2-butyne

Rotational transitions of the μ_a and μ_b type have been identified with microwave-microwave double resonance measurements for 1-chloro-2-butyne in the ground vibrational state. In the first excited state of the methyl torsion only μ_a-type transitions have been identified. The A-type transitions of the ground vibrational state can be described perfectly by the rigid rotor approximation with centrifugal corrections. Using the internal axis method the barrier to internal rotation was determined from the A,E splittings: V₃ = 10.05 ± 0.09 cm⁻¹. A model which allowed for geometry relaxation upon internal rotation was used to fit one set of parameters to the transition frequencies of both ground state and first excited torsional state. The sixfold contribution to the barrier was found to be negligible: V₆ = −0.4 ± 0.3 cm⁻¹.     

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).     

The 14N quadrupole coupling constants and barrier to internal rotation of ethylcyanide-d5

The microwave spectrum of ethylcyanide-d₅ has been recorded from 18.0 to 40.0 GHz. Both a-type and b-type transitions were observed and assigned. Also, the R-branch assignments have been made for three excited states of the internal torsional mode and two excited states of the CN inplane bending mode as well as an excited vibrational state involving both of these motions. The barrier to internal rotation was determined to be 3.00 ± 0.15 kcal/mole from the E, A splittings of the third excited state. The quadrupole coupling constants of the¹⁴N nucleus were found to have values of ?3.213, 1.168, and 2.045 MHz for χ_aa, χ_bb, and χ_cc, respectively. These results are compared to those previously obtained on the corresponding hydrogen compound.     

Torsional frequency,barrier to internal rotation,and dipole moment of N-sulphinylaniline from microwave rotational spectra

Microwave spectra of the ground and first three excited torsional states of N-sulphinylaniline have been assigned. The variation of the inertial defect with torsional number shows the molecule to be planar. The torsional frequency has been determined as ν = 41.1 cm^?1 and the barrier to internal rotation as V₂ = 2.3 kcal/mole. From the splittings of the Stark lobes of some lines the values μ_a = 2.20 ± 0.06, μ_b = 0.664 ± 0.005, and μ_tot = 2.30 ± 0.06 were obtained.     

Microwave spectra of dimethylsulfide-d6, (CD3)2S,ground and excited torsional states

The microwave spectra of the molecular isotope (CD₃)₂S in the ground state and the first and second excited states of methyl top torsion (internal rotation) and of CSC deformation as well as the ground-state spectra of the ¹³C and ³⁴S substituted forms have been measured. The rotational constants and centrifugal distortion and rotation-vibration interaction constants could be determined. The rotational lines in the excited torsional states (1₁, 1₂, 2₁, 2₂, 2₃) were found to be split into quartets due to the interaction between molecular rotation and methyl top internal rotation. The experimental multiplet splittings were fitted to those calculated from a rotation-internal rotation Hamiltonian in order to obtain values for the internal rotation barrier V₃ and the top-top interaction potential coefficients V₁₂ and V′₁₂. V₁₂ was too highly correlated with V₃ for a separate determination. The values following from the least-squares adjustment are discussed.     

The microwave spectrum of trans 1-nitropropene

Rotational transitions of 1-nitropropene arising from the ground vibrational state and from three excited states of the nitro torsional vibration have been assigned. The values of the rotational constants in MHz are: A₀=10 650B₀=2028.56C₀1722.16A₁10 615 B₁=2028.47 C₁=1725.11 A₂10 570 B₂ 2028.31 C₂= 1727.32 A₃= 10 512 B₃2028.11 C₃=1729.37The dipole moment components are μ_a = 4.52 D, μ_b = 0.42 D and μ_total = 4.54 D. From the lack of observable internal rotation splittings the barrier to internal rotation of the methyl group is shown to be greater than 2250 cal/mole.     

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.     

Analysis of the microwave spectrum of hydrazine

Microwave measurements in the interval from 6 to 133 GHz, consisting of 444 rotational transitions in the vibrational ground state of hydrazine with J ≤ 31 and K_a ≤ 6 were fit to an effective rotational Hamiltonian containing 9 asymmetric rotor constants, 14 NH₂ inversion parameters, and 1 internal rotation parameter, with an overall standard deviation of the fit of 0.40 MHz. This set of parameters contains: (i) the three rotational constants; (ii) tunneling splitting constants for NH₂ inversion at one end of the molecule, for NH₂ inversion at both ends of the molecule, and for internal rotation through the trans barrier; (iii) two K-type doubling constants affecting the K = 1 levels; (iv) an a-type Coriolis interaction with matrix elements linear in K; and (v) various centrifugal distortion corrections to the above parameters. A consistent group theoretical formalism was used to label the energy levels and to select terms in the phenomenological rotational Hamiltonian. The Hamiltonian matrix, which is set up in a tunneling basis set, is of dimension 16×16 and contains only ΔK_a = 0 matrix elements, asymmetric rotor effects being taken into account on the diagonal by terms from a Polo expansion in bⁿ. Hyperfine splittings and barrier heights are not discussed.     

Rotational spectrum, structure and internal rotation in CH3CCl3

The rotational spectra of the v₆ = 1 and v₆ = 2 torsional states of CH₃C³⁵Cl₃ have been measured in the millimeterwave range and accurate spectroscopic constants have been determined. The equilibrium structure, the torsional frequency and the barrier to internal rotation have been calculated ab initio. These results are shown to be compatible with the absence of splittings in the rotational spectra.     

Use of the anomalous Stark effect for the approximate determination of torsional energy splittings

An advantageous use of the anomalous Stark effect for the determination of the torsional energy splittings is proposed. The method is applicable in those cases where the dipole moment component connecting the torsional states of different parity has an experimentally observable magnitude. The analysis of the Stark spectrum observed in the spectrum of the N-cis lone-electron-pair gauche isomer of allylamine is presented as an example. The Stark effects of those transitions (a-type and b-type) which are inside the same vibrational state (0⁺ and 0^?), are used for the fitting of the μ_a, μ_b, and μ_c dipole moment components as well as the torsional energy splitting Δν_tors. The values obtained are compared to more accurate values derived by other methods. The possible use for predicting large torsional splittings is discussed.     

Microwave spectra and internal rotation in α-angelicalactone

The rotational spectrum of α-angelicalactone has been analyzed in the frequency range 18.0–40.0 GHz. The internal rotation barrier of the methyl group has been determined in the ground and four vibrationally excited states from the A-E splittings. The results indicate a possible rotational between the methyl torsion and the ring puckering mode. The ground state rotational parameters are consistent with a planar ring skeleton. The dipole moment components obtained from Stark displacements are μ_a = 3.16(1) D and μ_b = 2.59(2) D with a total value of 4.08(2) 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.     

Rotational and vibrational temperatures of electronically excited BiN radicals in a chemiluminescent flame

Rotational and vibrational temperatures of electronically excited BiN radicals in a low-pressure Bi_x+N/N₂*/N₂+Ar chemiluminescent flame have been deduced from high-resolution Fourier-transform emission spectra. Bands of three electronic transitions, a³Σ⁺(a₁1)→X¹Σ⁺(X0⁺), b⁵Σ⁺(b₁0⁺)→X¹Σ⁺(X0⁺), and b⁵Σ⁺(b₁0⁺)→a ³Σ⁺(a₁1), were analysed to determine the optical temperatures in the a³Σ⁺(a₁1) and b⁵Σ⁺(b₁0⁺) states. The rotational temperatures characterising the rotational populations in the a₁1, v=0 and 1 states were determined from the a₁→X, 0-2, 0-3, 0-4, 1-1, and 1-2 bands. The b₁→X, 0-8 and 0-11 bands, and the b₁→a₁, 0-0 bands served to determine the rotational temperature of the radicals in the b₁0⁺, v=0 state. The temperatures derived from the various bands and transitions were well consistent and the mean rotational temperature was determined to be 353±18 K, which is close to the translational temperature of the gas.Vibrational temperatures of the radicals in the a₁1 and b₁0⁺ states were derived from band intensities of the a₁→X and from the b₁→X as well as b₁→a₁ systems, respectively. The Franck-Condon factors needed were calculated with RKR potentials deduced from literature values of the rotational and vibrational constants in the three states involved. The a₁1 vibrational temperature (336±21 K) was close to the rotational temperature, while the b₁0⁺ vibrational temperature (438±36 K) differed, likely due to the previously observed perturbation of the b₁0⁺ state.     

The b-type rotational transitions of HNCO in the lowest excited vibrational state

In the microwave and millimeter wave spectra of HNCO, the b-type transitions between the K_a = 0 and 1 levels in the lowest excited vibrational state have been observed. Because of strong a-type Coriolis resonances among the three bending excited states the energy difference between the levels for K_a = 0 and 1 is much smaller in the lowest excited state than in the ground state. The subband origin of these b-type transitions has been found in the millimeter wave region at 275 697.309 MHz (9.1963 cm^?1). The effect of the Coriolis resonances is discussed in relation to the molecular quasi-linearity and is compared with the case of HNCS.     

The rotational spectra of the 79, 69, and 7 vibrational states of nitric acid

The rotational spectra of the first three vibrational states of nitric acid above 1000 cm⁻¹, 7¹9¹, 6¹9¹, and 7², have been measured and analyzed. The 7² state, along with the previously published 7¹ state, show the rotational and centrifugal distortional constants have a near linear dependence on the υ₇ vibrational quantum number. Large changes for several centrifugal distortion constants of the υ₇ = n series of states are attributed to a c-type Coriolis resonance manifold between the ν₇ and ν₆ vibrational modes and the Hamiltonian reduction and representation used to fit the spectra. The 7¹9¹ and 6¹9¹ states have torsional splittings of 12.361(8) and 22.47(1) MHz, respectively. These splittings are large compared to 2.340(8) MHz of the 9¹ state and can be explained by a ∼1-2% mixing through anharmonic Fermi resonances with the 9³ state, which has a large torsional splitting of ∼1760 MHz. The millimeter/submillimeter-wave spectrum of each state was fit separately to the experimental uncertainty of the measurements. The resultant rotational constants, distortional constants and inertial defects agree well with DFT calculations.     

The millimeter wave spectrum of tertiary butyl fluoride

Rotational spectra of tertiary butyl fluoride (TBF) in the ground and excited vibrational states have been recorded and analyzed. The excited state spectra show large splittings due to l resonance and the effect of the 2, -1 term r_t. Coriolis constants have been obtained for the three lowest degenerate states. An accidental resonance enabled the determination of the axial rotational constant of TBF.     

Fluorescence and fluorescence excitation spectra of jet-cooled carbazole

The fluorescence excitation spectra of jet-cooled carbazole molecules at vibrational temperatures of 55 and 80 K and the fluorescence spectrum of these molecules excited by radiation at the frequency of a pure electronic transition are measured. As the vibrational temperature increases, the excitation spectra exhibit a series of lines of the same symmetry, which are caused by the interaction of the active vibration with a subensemble of optically inactive vibrations. The final symmetry of the totally and nontotally symmetric vibrations is determined from the shape of the rotational contours of the lines of vibronic transitions. The values of a decrease in the frequency of the nontotally symmetric vibrations in the first excited electronic state S ₁ due to their interaction with the electronic state S ₂ are calculated to be up to 100 cm^?1. The frequencies of the pure electronic transitions in the absorption and fluorescence spectra coincide with each other and are equal to 30809 cm^?1, the frequencies of vibrations in the ground state S ₀ exceeding the frequencies of the corresponding vibrations in the excited state S ₁. The degree of polarization of the integral fluorescence is determined for a series of vibronic transitions of the a ₁ and b ₂ final symmetry that are observed in the fluorescence excitation spectra, and the contribution of the intensity with the borrowed polarization θ_⊥ to the integral fluorescence is calculated. It is found that the intensity θ_⊥ is higher for the transitions of the b ₂ symmetry and can reach ≈50%.     

A frequency analysis of the ν9 band of CD3CD3: experiment and ab initio calculations

The infrared gaseous spectrum of CD₃CD₃ has been measured in the range of 530–670cm^?1 to investigate vibration—torsion effects in the ν₉ band. Three separate spectra all taken under different experimental conditions were recorded. The lines with (ΔK = ?1) and with high values of K show torsional splittings that are substantially larger than expected from the observed barrier height. These splittings are caused primarily by Coriolis-type interactions between the torsional stack of ν₉ = 1 and the corresponding stack for the ground vibrational state. Because of a near-degeneracy that exists between the states (ν₉ = 0, ν₄ = 3) and (ν₉ = 1, ν₄ = 0), three subbands (K, σ) = (15,1), (16,2), (17,3) are resonantly perturbed. For these cases, perturbation-allowed 3ν₄ torsional transitions have been identified. Here σ= 0, 1, 2 or 3 labels the torsional sublevels. Measurements from the ν₉ and 3ν₄ bands, frequencies from the far-infrared torsional spectra in the ground vibrational state, and lower state combination differences from the ν₉ + ν₄ ? ν₄ band were fitted to within experimental uncertainty using an effective Hamiltonian which considered three torsional stacks; one for the ground vibrational state and two for ν₉ = 1. In all, 22 parameters were determined using a total of 2001 lines. Of these, three parameters were the interstack couplings, eight are from the ground vibrational state and 11 are from the excited vibrational state. Two barrier-dependent torsion—rotation parameters, which were essential for obtaining a satisfactory fit, were calculated by ab initio methods.     

Internal rotation in methyl silane by avoided-crossing molecular-beam spectroscopy

The avoided-crossing molecular-beam electric-resonance technique was applied to methyl silane in the ground torsional state. A new type of anticrossing is introduced which breaks the torsional symmetry and obeys the selection rules ΔJ = 0, K = +1 /a3 ?1. For these “barrier” anticrossings, the values of the crossing fields E_c yield directly the internal rotation splittings; the E_c are independent of the difference (A-B) in the rotational constants. Such anticrossings were observed for J from 1 to 6. Studies were also conducted of several “rotational” anticrossings (J, K) = (1, ±1) /a3 (2, 0) for which E_c does depend on (A-B). The normal rotational transition (J, K) = (1, 0) ← (0, 0) was observed in the ground torsional state using the molecular beam spectrometer. The present data on CH₃²⁸SiH₃ were combined with Hirota's microwave spectra and analyzed with the torsion-rotation Hamiltonian including all quartic centrifugal distortion terms. In addition to evaluating B and several distortion constants, determinations were made of the moment of inertia of the methyl top I_α = 3.165(5) amu-Ų, the effective rotational constant A^eff = 56 189.449(32) MHz, and the effective height of the threefold barrier to internal rotation V₃^eff = 592.3359(73) cm^?1. The correlations leading to these two effective constants are discussed and the true values of A and V₃ are determined within certain approximations. For the isotopic species CH₃³⁰SiH₃, barrier and rotational anticrossings were observed. The isotopic changes in A and V₃ were determined, as well as an upper limit to the corresponding change in I_α.     

The rotational spectrum of methoxyethyne: Centrifugal distortion and internal rotation analysis

In the rotational spectrum of methoxyethyne 173 new transitions (J ≤ 30) have been measured between 150 and 240 GHz. In the centimeter range 25 new transitions (J ≤ 11) of the first excited torsional state have also been assigned. An overall fit of the measurements using a structure relaxation model has allowed us to accurately determine the internal rotation parameters. For the A substate effective rotational parameters are given which allow the calculation of transition frequencies of possible astrophysical interest.