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.     

Microwave spectrum of (CH3)3CCN-SO3

Eight rotational transitions of the complex (CH₃)₃CCN-SO₃ have been recorded using pulsed-nozzle Fourier transform microwave spectroscopy and a series of ab initio calculations has been performed. The complex is a symmetric top with free or nearly free internal rotation of the SO₃ and (CH₃)₃CCN subunits. The nitrogen-sulfur bond distance is determined to be 2.394(19) Å. Calculations at the MP2/aug-cc-pVTZ level/basis, which are in excellent agreement with the experimental results, give a binding energy of 11.0 kcal/mol relative to (CH₃)₃CCN and SO₃. Physical properties of the system, including N-S bond length, N-S-O angle, binding energy, and the degree of electron transfer (obtained from Townes and Dailey analysis of the ¹⁴N nuclear quadrupole coupling constant) are compared with those of similar complexes. The proton affinity of the base is a useful parameter for ordering complexes in the series.     

Methyl group tilt and structure from rotational spectra of the CH2DNHCl monodeuterated species

The structure and tilt of the methyl group of CH₃NHCl have been determined by analysis of the three different ground state rotational spectra of the methyl monodeuterated species. The tilt was found to be ?3.5° which is of the same order of magnitude and towards the unshared pair of electrons at the nitrogen atom as in methylamine and its derivatives.The barrier to internal rotation was determined form the A-E splittings of the previously measured transitions and found to be 3781 ± 14 cal/mole for CH₃NHCl and 3784 ± 15 cal/mole for CH₃NDCl, while the values obtained under the assumptions of no tilt and of asymmetric methyl group as in methylamine were 3707 ± 30 cal/mole for CH₃NHCl and 3726 ± 25 cal/mole for CH₃NDCl. Some information has also been deduced on the orientation of the z axis of the principal quadrupole coupling tensor.     

Perturbation of the internal vibrations of (CH3)2S and (CH3)2Se in matrix-isolated complexes with H2O and HCl: Indirect evidence for the trans lone pair effect in (CH3)2X molecules

The formation of hydrogen-bonded complexes (CH₃)₂X ? HA is characterized by small frequency perturbations of the internal vibrations of the base molecules in a low-temperature matrix. Apart from the ν_CXC vibrations the largest shifts are measured in the ν_CH3 spectral region. The unexpected large blue shifts, Δν_CH, are interpreted as an indirect evidence for the existence of the trans lone pair effect in methyl chalcogenides. Additional support is obtained from a comparison between the complexes of HCl and H₂O with (CH₃)₂O, (CH₃)₂S, and CH₃OH.     

Millimeter-wave spectrum and internal rotation of 1-silylpropyne,CH3CCSiH3

Rotational transitions of CH₃CCSiH₃ have been observed in the millimeter-wave region using a computer-controlled source-frequency modulation spectrometer with a 1.8-m-long free space absorption cell. The observed spectrum clearly showed the effect of internal rotation with a small potential barrier. It has been analyzed by calculating the torsion-rotation energies on the basis of torsional wave functions obtained by diagonalizing the torsional part of the Hamiltonian. The least-squares analysis has yielded the rotational constant B = 2068.2817(4) MHz and a few centrifugal distortion constants. The barrier height to internal rotation has been determined to be 3.77(70) cm^?1 from the contour map of the standard deviation. Also, the A rotational constant of the silyl group around the symmetry axis has been estimated by fixing the A constant of the methyl group to the value of CH₃CCH.     

Internal Rotation, Quadrupole Coupling, and Structure of (CH3)3SiCl Studied by Microwave Spectroscopy and ab Initio Calculation

The microwave spectrum of (CH₃)₃SiCl and its isotopic species (CH₃)₃Si³⁷Cl, (CH₃)₃²⁹SiCl, (CH₃)₃³⁰SiCl, and (¹³CH₃)(CH₃)₂SiCl has been studied in the frequency range of 3 to 40 GHz. The barrier to internal rotation, the chlorine quadrupole coupling, and the structure were determined. Ab initio calculation were compared with the experimental results.     

The microwave spectrum, structure, and barrier to internal rotation of selenoacetaldehyde, CH3CHSe

The rotational spectrum of the unstable molecule selenoacetaldehyde, CH₃CHSe, has been studied by microwave spectroscopy between 26.5 and 40 GHz. Transitions have been measured for five abundant selenium isotopic variants. These measurements have, together with structural information from the related molecules CH₃CHS and CH₃CHO, allowed reliable data on the C=Se bond length (1.758 ± 0.01 Å) and the e angle (125.7 ± 0.3°) to be derived. The spectral lines show splittings due to hindered internal rotation and using these together with the derived structure, barrier heights of 1602 cal mole⁻¹ (6703 J mole⁻¹) and 1648 cal mole⁻¹ (6859 J mole⁻¹) have been determined for the ground and first torsionally excited states, respectively.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

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.     

PAM analysis of the microwave spectra of thioacetic acid,CH3COSH and CH3COSD

The microwave spectra of two isotopic species of thioacetic acid, CH₃COSH and CH₃COSD, have been studied. Using the principal axis method (PAM), including terms through n = 6 in the perturbation series and the denominator correction, the spectra were analyzed and 45 lines for CH₃COSH and 40 lines for CH₃COSD were assigned. The parameters obtained by the least-squares analysis are A = 9913.29 ± 0.56 MHz, B = 4923.11 ± 0.23 MHz, C = 3354.60 ± 0.24 MHz, θ = 57.080 ± 0.030°, s = 6.2980 ± 0.0012, and I_α = 3.198 ± 0.020 amu$\text{A}\text{?}{}^2$ for CH₃COSH, and A = 9662.80 ± 0.78 MHz, B = 4810.74 ± 0.26 MHz, C = 3273.92 ± 0.18 MHz, θ = 55.097 ± 0.024°, s = 5.9742 ± 0.0016, and I_α = 3.171 ± 0.020 amu$\text{A}\text{?}{}^2$ for CH₃COSD. The barrier to internal rotation of the methyl group is V₃ = 222.6 ± 1.4 cal/mole for CH₃COSH and V₃ = 212.9 ± 1.4 cal/mole for CH₃COSD. The Stark effect measurements of A species transitions for CH₃COSH led to the dipole moment μ = 1.821 ± 0.013 D with the components μ_a = 0.191 ± 0.010 D and μ_b = 1.811 ± 0.013 D.     

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.     

Quasi-symmetric top molecule approach to the rotational-vibrational problem of CH3XY molecules: Application to CH3OD

The quasi-symmetric top molecule approach proposed previously [J. Koput, J. Mol. Spectrosc.104, 12–24 (1984)] to calculate vibration-rotation energy levels of a CH₃XY molecule is used to study the COD bending-torsion-rotation energy levels of monodeuterated methanol, CH₃OD. The available 150 transition frequencies (microwave, millimeter wave, and infrared data) have been fitted and the barrier to linearity of the COD skeleton has been found to be about 7000 cm^?1. The effective barrier to internal rotation in the ground state has been determined to be 365.79 cm^?1 and that in the first excited state of the COD bending mode has been predicted to be 380.62 cm^?1.     

The microwave spectrum,substitution structure,internal rotation barrier,and dipole moment of thioacetaldehyde,CH3CHS

The microwave rotational spectrum of the unstable species thioacetaldehyde, CH₃CHS, has been studied in a flow pyrolysis system. Eight isotopic variants have been studied allowing an accurate substitution structure to be derived. Most of the spectral lines show splittings due to internal rotation, analysis of which has allowed a barrier study to be made. For the torsional ground state of the most abundant species, V₃ = 1572 ± 30 cal/mole or 375.7 ± 7 J/mole. The dipole moment is μ = 2.33 ± 0.02 D with components μ_A = 2.26 ± 0.02 and μ_B = 0.56 ± 0.01 D.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic 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.     

Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH

Kinetics and mechanisms for reactions of OH with methanol and ethanol have been investigated at the CCSD(T)/6-311 + G(3df, 2p)//MP2/6-311 + G(3df, 2p) level of theory. The total and individual rate constants, and product branching ratios for the reactions have been computed in the temperature range 200-3000 K with variational transition state theory by including the effects of multiple reflections above the wells of their pre-reaction complexes, quantum-mechanical tunneling and hindered internal rotations. The predicted results can be represented by the expressions k₁ = 4.65 × 10⁻²⁰ × T^2.68 exp(414/T) and k₂ = 9.11 × 10⁻²⁰ × T^2.58 exp(748/T) cm³ molecule⁻¹ s⁻¹ for the CH₃OH and C₂H₅OH reactions, respectively. These results are in reasonable agreements with available experimental data except that of OH + C₂H₅OH in the high temperature range. The former reaction produces 96-89% of the H₂O + CH₂OH products, whereas the latter process produces 98-70% of H₂O + CH₃CHOH and 2-21% of the H₂O + CH₂CH₂OH products in the temperature range computed (200-3000 K).     

New analysis of the Coriolis-interacting v2 and v5 bands of CH3Br and CH3Br

The and fundamental bands of CH₃⁷⁹Br and CH₃⁸¹Br have been studied by Fourier transform infrared spectroscopy with an unapodized resolution of 0.004 cm⁻¹, corresponding to an improvement of one order of magnitude compared to previous studies. For both isotopomers, some 2427 (2239) lines were newly assigned for the parallel and the perpendicular bands and, in addition, 80 perturbation-allowed transitions were also added. The ground-state axial rotational constants A₀ were redetermined from allowed and perturbation-allowed infrared transitions observed in the v₂ and v₅ bands around the local crossing. The A₀ values obtained for both isotopomers are more accurate but fully compatible with those obtained previously. Using those results, and the variation of the rotational constants with vibration, new accurate equilibrium constants A_e and B_e have been also determined for CH₃⁷⁹Br and CH₃⁸¹Br. The excited states v₂=1 and v₅=1 are coupled by Coriolis-type interactions (Δl=±1,ΔK=±1) and (Δl=?1,ΔK=±2), while the l₅=±1 levels of v₅ interact also through “l(2,2)”-type interaction (Δl=±2,ΔK=±2). The Coriolis coupling term was determined to be for CH₃⁷⁹Br and for CH₃⁸¹Br. All interaction parameters have been determined with higher accuracy, compared to previous studies. A total of 4213 (3704) line positions with J?68(64) and K?16(11) including all available data was fitted using 20 (18) parameters with a root-mean-square deviation of 0.0007 (0.0006) cm⁻¹ for CH₃⁷⁹Br and CH₃⁸¹Br, respectively. Two different but equivalent forms of reduced Hamiltonians with two different sets of constrained constants were successfully applied according to Lobodenko's reduction [J. Mol. Spectrosc. 126 (1987) 159]. The ratio of the transition moments, |d₂/d₅|=1.65, and a positive sign of the Coriolis intensity perturbation d₂×ζ₂₅×d₅ were determined. Therefore, it has been possible to generate an accurate prediction of the whole spectrum between 1200 and 1650 cm⁻¹, including Q branches.     

High-Resolution Far-Infrared Torsional Spectrum of CH3SiD3 Using a Synchrotron Source

The far-infrared torsional spectrum of CH₃SiD₃ has been measured in a continuing effort to quantify the coupling between the small amplitude vibrations and the large amplitude internal rotation of the methyl group in symmetric tops. It is hoped that this will help in understanding the role of torsional motion in intramolecular vibrational relaxation. The spectrum was recorded with the Bruker IFS120 HR interferometer that is coupled to the MAX-I synchrotron radiation source in Lund, Sweden. High-resolution (0.002 cm⁻¹) spectra of the very weak torsional overtone 2ν₆ and hot band 3ν₆−ν₆ were recorded between 230 and 350 cm⁻¹. A total of 1413 frequencies in these two bands were assigned. In a separate experiment, a high-resolution (0.00125 cm⁻¹) spectrum of the lowest-lying degenerate fundamental band ν₁₂ was measured between 360 and 480 cm⁻¹, and 3263 frequencies belonging to this band were assigned. This spectrum was recorded with the Bruker IFS120 HR interferometer located at the University of Oulu, Finland. The frequencies from the aforementioned three bands and the data from the recent molecular beam measurements reported by Ozier and Meerts (J. Chem. Phys.109, 4823 (1998)) were analyzed using a model which considered three interacting torsional stacks: one for the ground vibrational state and two for v₁₂=1. A fit to within the experimental error was obtained by varying 36 molecular parameters. Several interstack coupling constants have been determined. A comparison of the leading parameters between CH₃SiD₃ and CH₃SiH₃ is presented.     

Far-infrared internal rotation spectrum of CH3OD and CD3OD

The far-infrared spectra of the Q branches of hindered rotation in CH₃OD and CD₃OD have been investigated in the 80- to 250-cm^?1 spectral region. The theoretical spectra are calculated using the full set of Kirtman constants and are compared with the experimental spectra of resolutions up to 0.13 cm^?1.     

Effects of an accidentally strong resonance in the rotational spectrum of CH3CN and CH3CN in the 2ν8 state

An accidentally strong resonance has been revealed in the rotational spectrum of the state v₈ = 2 in each of the two molecules CH₃C¹⁴N and CH₃C¹⁵N. This resonance occurs between the energy levels l = 0, K = ±4 and l = ±2, K = ?2. A calculation of the effect of this resonance has led to the assignment of the corresponding absorption lines and finally to the evaluation of new molecular constants, including the value of the separation between the two levels which are perturbed by the resonance.