Vibrational spectroscopic studies,conformations and ab initio calculations of 1,2‐bis(trifluorosilyl)ethane (SiF3CH2CH2SiF3)

Infrared spectra of 1,2‐bis(trifluorosilyl)ethane (SiF₃CH₂CH₂SiF₃) were obtained in the vapour and liquid phases, in argon matrices and in the solid phase. Raman spectra of the compound as a liquid were recorded at various temperatures between 293 and 270 K and spectra of an apparently crystalline solid were observed. The spectra revealed the existence of two conformers (anti and gauche) in the vapour, liquid and in the matrix. When the vapour was chock‐frozen on a cold finger at 78 K and annealed to 150 K, certain weak Raman bands vanished in the crystal. The vibrational spectra of the crystal demonstrated mutual exclusion between IR and Raman bands in accordance with C_2h symmetry. Intensity variations between 293 and 270 K of pairs of various Raman bands gave ΔH(gauche—anti) = 5.6 ± 0.5 kJ mol⁻¹ in the liquid, suggesting 85% anti and 15% gauche in equilibrium at room temperature. Annealing experiments indicate that the anti conformer also has a lower energy in the argon matrices, is the low‐energy conformer in the liquid and is also present in the crystal. The spectra of both conformers have been interpreted, and 34 anti and 17 gauche bands were tentatively identified. Ab initio and density functional theory (DFT) calculations were performed giving optimized geometries, infrared and Raman intensities and anharmonic vibrational frequencies for both conformers. The conformational energy difference derived in CBS‐QB3 and in G3 calculations was 5 kJ mol⁻¹. Copyright © 2009 John Wiley & Sons, Ltd.     

Conformational,vibrational, and structural studies of 2,2,3,3,3‐pentafluoropropylamine from Raman and infrared spectra of gas,liquid, xenon solutions,and solid supported by ab initio calculations

The Raman and infrared spectra (3500–50 cm⁻¹) of the gas, liquid or solution, and solid were recorded of 2,2,3,3,3‐pentafluoropropylamine (CF₃CF₂CH₂NH₂) and the ND₂ isotopomer. Variable temperature (−55 to − 100 °C) studies of the infrared spectra (3600–400 cm⁻¹) of samples dissolved in liquid xenon have been carried out. From these data, two of the five possible conformers have been identified and their relative stabilities obtained. The enthalpy difference was determined between the more stable Tt conformer and the less stable Tg form to be 280 ± 14 cm⁻¹ (3.35 ± 0.17 kJ/mol). The first indicator is the NCCC dihedral angle (G = gauche or T = trans), and the second one (g = gauche or t = trans) is the relative position of the lone pair of electrons on nitrogen with respect to the β‐carbon. The percentage of the Tg conformer at ambient temperature is estimated to be 34 ± 2%. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug‐cc‐pVTZ for both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for most of the observed bands for both isotopomers, supported by MP2(full)/6‐31G(d) ab initio calculations to predict the harmonic force fields, wavenumbers, infrared intensities, Raman activities, and depolarization ratios for both conformers. Estimated r₀ structural parameters were obtained from adjusted MP2(full)/6‐311 + G(d,p) calculations. The results are discussed and compared with the corresponding properties of some related molecules. Copyright © 2011 John Wiley & Sons, Ltd.     

Infrared and Raman Spectra,conformations, ab initio calculations and spectral assignments of 1,3‐disilabutane (SiH3CH2SiH2CH3)

Raman spectra of 1,3‐disilabutane (SiH₃CH₂SiH₂CH₃) as a liquid were recorded at 293 K and as a solid at 78 K. In the Raman cryostat at 78 K an amorphous phase was first formed, giving a spectrum similar to that of the liquid. After annealing to 120 K, the sample crystallized and large changes occurred in the spectra since more than 20 bands present in the amorphous solid phase vanished. These spectral changes made it possible to assign Raman bands to the anti or gauche conformers with confidence. Additional Raman spectra were recorded of the liquid at 14 temperatures between 293 and 137 K. Some Raman bands changed their peak heights with temperature but were countered by changes in linewidths, and from three band pairs assigned to the anti and gauche conformers, the conformational enthalpy difference Δ_confH(gauche–anti) was found to be 0 ± 0.3 kJ mol⁻¹ in the liquid. Infrared spectra were obtained in the vapor and in the liquid phases at ambient temperature and in the solid phases at 78 K in the range 4000–400 cm⁻¹. The sample crystallized immediately when deposited on the CsI window at 78 K, and many bands present in the vapor and liquid disappeared. Additional infrared spectra in argon matrixes at 5 K were recorded before and after annealing to temperatures 20–34 K. Quantum chemical calculations were carried out at the HF, MP2 and B3LYP levels with a variety of basis sets. The HF and DFT calculations suggested the anti conformer as the more stable one by ca 1 kJ mol⁻¹, while the MP2 results favored gauche by up to 0.4 kJ mol⁻¹. The Complete Basis Set method CBS‐QB3 gave an energy difference of 0.1 kJ mol⁻¹, with anti as the more stable one. Scaled force fields from B3LYP/cc‐pVQZ calculations gave vibrational wavenumbers and band intensities for the two conformers. Copyright © 2007 John Wiley & Sons, Ltd.     

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.     

Microwave spectroscopic study of the conformations,relative energies,and dipole moments of ethyl cyanoformate

The microwave spectrum of ethyl cyanoformate displays a-type band spectra from three nearly prolate conformers. High-resolution spectra of the two more stable species have been assigned. One form, designated extended, has rotational constants A″ = 6453.3(4) MHz, B″ = 1500.47(6) MHz, C″ = 1236.36(6) MHz, which are consistent with a syn-anti [τ₁ (OCOC) = 0°, τ₂ (COCC) = 180°] structure. The second form, labeled compact, has rotational constants A″ = 6787.8(7) MHz, B″ = 1549.38(8) MHz, C″ = 1406.80(8) MHz, which are consistent with a syn-gauche [τ₁ (OCOC) = 0°, τ₂ (COCC) ～ 90°] structure. The extended form is marginally more stable, ΔE = 55 ± 27 cm^?1. The extended conformer has dipole moment components μ_a = 4.44(7), μ_b ～ 0 D and the compact conformer has dipole moment components μ_a = 4.25(7), μ_b = 0, μ_c = 1.08(23) D. The third conformer (relative energy 600 ± 140 cm^?1) has the most intense band series even at ?63°C. the bands of this conformer are unresolvable into individual rotational transitions.     

Microwave spectral studies of rotational isomerism in substituted ethanethiols: 2-Aminoethanethiol and 2-chloroethanethiol

Microwave spectra were observed and analyzed for 2-aminoethanethiol and 2-chloroethanethiol. The amino compound exists in two gauche rotameric conformations, one exhibiting an intramolecular SH?N hydrogen bond. The hydrogen-bonded conformer lies higher in energy by 274 ± 90 cal mole^?1 and has the following rotational constants (in MHz): A = 12 040.1 ± 11.3, B = 3352.24 ± 0.03, and C = 2881.99 ± 0.03. For the non-hydrogen-bonded conformer the rotational constants (in MHz) are A = 11 929.9 ± 10.2, B = 3395.01 ± 0.03, and C = 2877.82 ± 0.03. Dipole moment measurements for the H-bond conformer led to μ_a = 2.68 D, μ_b = 0.88 D, and μ_c = 0.37 D, while for the non-H-bond form the values are μ_a = 1.51 D, μ_b = 0.0 D, and μ_c = 0.62 D. In the case of chloroethanethiol, the only assigned spectral lines were the unresolved J → J + 1 a-type bands of a trans conformation. For this molecule the combination rotational constant B + C has the value 2955.17 ± 0.02 MHz for the ³⁵Cl species and 2879.73 ± 0.02 MHz for the ³⁷Cl species.     

Raman and infrared spectra,conformational stability,vibrational assignment,barriers to internal rotation and ab initio calculations of but-2-enoyl chloride

The Raman (3500–10 cm⁻¹) and infrared (3200–50 cm⁻¹) spectra were recorded for the fluid and solid phases of but-2-enoyl chloride (crotonyl chloride), trans-CH₃CHCHCClO, where the methyl group is trans to the CClO group, and a complete vibrational assignment is proposed. These data were interpreted on the basis that the s-trans (anti) form (two double bonds oriented trans to one another) is the most stable form in the fluid phases and the only conformer remaining in the solid state. The asymmetric torsional fundamental of the more stable s-trans and the higher energy s-cis (syn) form were observed at 97.5 and 86.9 cm⁻¹, respectively. From these data the asymmetric potential function governing the internal rotation about the C C bond was determined. The potential coefficients are V₁ = −111 ± 2, V₂ = 1860 ± 48, V₃ = 6 ± 2, V₄, = −43 ± 24 and V₆ = −22 ± 6. The s-trans to s-cis and s-cis to s-trans barriers were determined to be 1890 and 1785 cm⁻¹, respectively, with an enthalpy difference between the conformers of 105 ± 52 cm⁻¹ [300 ± 149 cal mol⁻¹ (1 cal = 4.184 J)]. Similarly, the barrier governing internal rotation of the CH₃ group for the s-trans conformer was also determined to be 912 ± 30 (2.61 ± 0.09 kcal mol⁻¹) from the torsional fundamental observed in the far-infared spectrum of the gas. All these data were compared with the corresponding quantities obtained from ab initio Hartree–Fock gradient calculations employing the RHF/3–21G*, RHF/6–31G* and/or MP2/6–31G* basis sets. These results were compared with the corresponding quantities for some similar molecules.     

The conformational analysis of 1-haloalkanes by low resolution microwave spectroscopy

The low resolution microwave spectra of a series of 1-haloalkanes were studied. With the exception of 1-bromobutane only the all s-trans conformer and those gauche conformers in which a single dihedral angle is gauche were foud. By analyzing data from a homologous series, a gauche dihedral angle of 286 ± 4° was determined for the gauche conformers of the bromo and iodo species. An analysis of relative intensities of the 1-bromobutane and 1-iodobutane bands yielded standard Gibbs free energy differences.     

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.     

Microwave spectrum and rotational isomerism of 3,3-difluoropropene CHF2CHCH2

The analysis of the microwave spectrum of 3,3-difluoropropene has confirmed the existence of two rotational isomers, cis and gauche. The rotational constants in the ground vibrational state are A = 9126.08 MHz, B = 3722.120 MHz, and C = 2946.598 MHz for the cis form and A = 8901.64 MHz, B = 4192.759 MHz, and C = 3107.718 MHz for the gauche form. The dipole moment and its components along the principal axes of intertia are μ_a = 2.369 ± 0.015 D, μ_c = 0.70 ± 0.03 D, and μ_t = 2.47 ± 0.03 D for the cis form and μ_a = 1.535 ± 0.015 D, μ_b = 0.53 ± 0.04 D, μ_c = 1.36 ± 0.03 D, and μ_t = 2.12 ± 0.05 D for the gauche form. The relative intensity measurement indicates that the cis form is more stable than the gauche form by 260 ± 80 cm^?1. The energy of the first excited state with respect to the ground state was found to be 63 ± 8 cm^?1 for the cis form and 85 ± 10 cm^?1 for the gauche form. Two Fourier coefficients of the potential function restricting the torsion around the CC bond were determined to be V₁ = 266 ± 40 cm^?1 and V₃ = 508 ± 200 cm^?1, using the available data. The potential function thus obtained is compared to a prediction model which is derived assuming additivity of the potential as a function of substitution.     

Internal rotation and molecular structure of ethaneselenol by microwave spectroscopy

The microwave spectra of ethaneselenol and its deuterated and ¹³C-substituted species were measured and assigned for the gauche and trans isomers. The double minimum splittings in the gauche isomers were directly observed for the species having a symmetry plane in the frame part. The rotational constants and the torsional splitting of the gauche isomer of the parent species were determined to be A = 27 148.86 ± 0.05, B = 3 623.68 ± 0.01, C = 3 399.21 ± 0.03, and Δν = 1 083.33 ± 0.04 MHz. From the torsional splittings of the parent and SeD species together with the vibrational frequencies already reported by Durig and Bucy, the Fourier coefficients of the selenol internal rotation potential function were determined to be V₁ = ?44 ± 17, V₂ = ?260 ± 3, V₃ = 1202 ± 16, and V₆ = ?43 ± 9 cal/mole. From the rotational constants obtained, the r_s structural parameters of the gauche and trans isomers were determined. The structural parameters in the skeletal part for the gauche isomer are $\text{r}\text{(CC) = 1.524}\text{A}\text{?}$, $\text{r}\text{(CSe) = 1.957}\text{A}\text{?}$, $\text{r}\text{(SeH) = 1.467}\text{A}\text{?}$, α(CCSe) = 113°31′, α(CSeH) = 93°05′, and the dihedral angle τ(CCSeH) = 61°39′. Those for the trans isomer are $\text{r}\text{(CC) = 1.525}\text{A}\text{?}$, $\text{r}\text{(CSe) = 1.962}\text{A}\text{?}$, $\text{r}\text{(SeH) = 1.440}\text{A}\text{?}$, α(CCSe) = 108°43′, and α(CSeH) = 93°30′. These parameters were compared with the corresponding ones of ethanethiol.     

The microwave spectrum of piperidine: Equatorial and axial ground states

The microwave spectra of piperidine and N-deuterated piperidine were investigated between 8 and 40 GHz. The ground states of both equatorial and axial conformers have been identified by both type-A and type-C transitions, and the substitution coordinates of the imino hydrogen have been determined for both conformers. Dipole-moment components for the equatorial conformer are μ_a = 0.178 D, μ_c = 0.80 D, μ = 0.82 D, and for the axial conformer are μ_a = 1.07 D, μ_c = 0.521 D, μ = 1.19 D. The quadrupole coupling constants for the axial conformer are: χ_aa = ?3.80 MHz, χ_bb = 2.91 MHz, χ_cc = 0.83 MHz and for the equatorial conformer χ_cc = ?4.83 MHz. The rotational constants indicate a significant flattening of the ring in axial piperidine compared with equatorial piperidine. The equatorial conformer is the more abundant; intensity measurements on several sets of lines indicate the excess energy of the axial conformer to be 3.1 ± 0.3 kJ mole^?1. This represents a significant change from our earlier reported value and is now more in line with measurements obtained by other methods.     

Conformational stability from Raman spectra,r0 structural parameters,and vibrational assignment of methylcyclohexane

The Raman spectra (3500–50 cm⁻¹) of the liquid and solid methylcyclohexane and the infrared spectra of the gas and solid methylcyclohexane have been recorded. The Raman band at 754 cm⁻¹ in the liquid has been confidently assigned to the less stable axial conformer and its intensity was recorded as a function of temperature from 25 to −95 °C. By the utilization of 15 different temperatures, the enthalpy difference between the more stable chair‐equatorial conformer and the chair‐axial form was determined to be 712 ± 71 cm⁻¹ (8.50 ± 0.84 kJ/mol). The ab initio predicted value of 710 cm⁻¹ (8.50 kJ/mol) from the MP2(full)/6‐311G(2d,2p) calculations with and without diffuse functions is in excellent agreement. The harmonic force fields, infrared intensities, Raman activities, depolarization ratios, and vibrational wavenumbers have been obtained for both conformers from MP2(full)/6‐31G(d) ab initio calculations. With two scaling factors of 0.88 for the C‐H stretches and 0.9 for the remaining ones, the fundamental wavenumbers have been predicted and along with the depolarization values and infrared band contours (B‐type for A″ modes) a complete vibrational assignment has been made for the chair‐equatorial conformer. Predicted r₀ structural parameters have been provided from adjusted parameters from ab initio MP2(full)/6‐311+G(d,p) calculations. The results are discussed and compared with the corresponding properties of some similar molecules. Copyright © 2009 John Wiley & Sons, Ltd.     

Microwave spectrum of gauche-isopropylphosphine

The microwave spectra of isopropylphosphine has been recorded in the region 12.4–40.0 GHz. Both a- and b-type transitions were observed and assigned. The rigid rotor rotational constants were determined to be A = 7633.34 ± 0.09, B = 4243.36 ± 0.02, and C = 3045.84 ± 0.02 MHz for (CH₃)₂CHPH₂ and A = 7226.47 ± 0.05, B = 4041.06 ± 0.02, and C = 2946.85 ± 0.02 MHz for (CH₃)₂CHPD₂. Dipole moment components of |μ_a| = 1.15 ± 0.01, |μ_b| = 0.43 ± 0.01, |μ_c| = 0.03 ± 0.02 and |μ_t| = 1.23 ± 0.01 were determined from the Stark effect. From the microwave spectra, the Stark effect and the experimental rotational constants, the assigned spectrum has been identified to result from the gauche form and this conformer is believed to be more stable than the other form which is present at room temperature.     

Conformational and structural studies of n‐propylamine from temperature dependent Raman and far infrared spectra of xenon solutions and ab initio calculations

The Raman and infrared spectra (4000 to 50 cm^–1) of the gas, liquid or solution, and solid have been recorded of n‐propylamine, CH₃CH₂CH₂NH₂. Variable temperature (−60 to −100 °C) studies of the Raman (1175 to 625 cm^–1) and far infrared (600 to 10 cm^–1) spectra dissolved in liquid xenon were carried out. From these data, the five possible conformers were identified and their relative stabilities obtained with enthalpy difference relative to trans–trans (Tt) for trans–gauche (Tg) of 79 ± 9 cm^–1 (0.9 ± 0.1 kJ/mol); for Gg of 91 ± 26 cm^–1 (1.08 ± 0.3 kJ/mol); for Gg′ of 135 ± 21 cm^–1 (1.61 ± 0.2 kJ/mol); for Gt of 143 ± 11 cm^–1 (1.71 ± 0.1 kJ/mol). The percentage of the five conformers is estimated to be 18% for the Tt, 24 ± 1% for Tg, 23 ± 3% for Gg, 18 ± 1% for Gg′ and 18 ± 1% for Gt at ambient temperature. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug‐cc‐pVTZ from both second‐order Møller–Plesset (MP2, full) and density functional theory calculations by the Becke, three‐parameter, Lee–Yang–Parr method. Vibrational assignments were provided for the observed bands for all five conformers, which are supported by MP2(full)/6‐31G(d) ab initio calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. Estimated r₀ structural parameters were obtained from adjusted MP2(full)/6‐311+G(d,p) calculations. The results are discussed and compared with the corresponding properties of some related molecules. Copyright © 2012 John Wiley & Sons, Ltd.     

Gas phase A-band short time photodissociation dynamics of trans and gauche conformations of 1-iodopropane and comparison with the solution phase short time photodissociation dynamics

A-band resonance Raman spectra are reported for gas phase 1-iodopropane. The gas phase absorption spectrum and resonance Raman intensities were simulated using time-dependent wavepacket calculations and a simple model in order to extract the A-band short time photo-dissociation dynamics for the trans and gauche conformers of 1-iodopropane. The gas phase short time dynamics for trans and gauche are very similar to the results obtained from a reanalysis of corresponding solution phase spectra. This indicates that solvation has little effect on the A-band short time photodissociation dynamics. However, the electronic dephasing parameters for the gauche conformer increase significantly upon solvation while the trans conformer parameters are almost the same in the gas and solution phases. This suggests that the gauche conformer in the A-band excited electronic state undergoes stronger interaction with the solvent than the trans conformer to give rise to faster electronic dephasing upon solvation for the gauche conformer.     

Raman and infrared,microwave spectra,conformational stability,adjusted r0 structural parameters,and vibrational assignments of cyclopentylamine

Fourier transform microwave spectrum of cyclopentylamine, c–C₅H₉NH₂ has been recorded, and seven transitions have been assigned for the most abundant conformer, and the rotational constants have been determined: A = 4909.46(5), B = 3599.01(4), and C = 2932.94(4). From the determined microwave rotational constants and ab initio MP2(full)/6‐311 + G(d,p) predicted structural values, adjusted r₀ parameters are reported with distances (Å): rC_α–C_β = 1.529(3), rC_β–C_γ = 1.544(3), rC_γ–C_γ = 1.550(3), rC_α–N = 1.470(3), and angles (°) ∠CCN = 108.7(5), ∠C_βC_αC_β = 101.4(5), and τC_βC_αC_β′C_γ′ = 42.0(5). The infrared spectra (4000–220 cm⁻¹) of the gas have been recorded. Additionally, the variable temperature (−60 to −100 °C) Raman spectra of the sample dissolved in liquefied xenon was recorded from (3800–50 cm⁻¹). The four possible conformers have been identified, and their relative stabilities obtained with enthalpy difference relative to t‐Ax of 211 ± 21 cm⁻¹ for t‐Eq ≥ 227 ± 22 cm⁻¹ for g‐Eq ≥ 255 ± 25 cm⁻¹ for g‐Ax. The percentage of the four conformers is estimated to be 53% for the t‐Ax, 11 ± 1% for t‐Eq, 20 ± 2% for g‐Ax and 16 ± 2% for g‐Eq at ambient temperature. The conformational stabilities have been predicted from ab initio calculations by utilizing several different basis sets up to aug‐cc‐pVTZ from both MP2(full) and density functional theory calculations by the B3LYP method. Vibrational assignments have been provided for the observed bands for all four conformers, which are predicted by MP2(full)/6‐31G(d) ab initio calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities, and depolarization ratios for all of the conformers. The results are discussed and compared to the corresponding properties of some related molecules. Copyright © 2014 John Wiley & Sons, Ltd.     

The microwave spectra,conformations, and dipole moments of 4-cyanocyclopentene

Microwave spectra have been observed and assigned for the axial and equatorial conformations of 4-cyanocyclopentene. For the axial species the rotational constants in megahertz are A = 5095.77, B = 2185.81, and C = 1936.50; for the equatorial species the values are A = 6762.66, B = 1916.72, and C = 1590.60. Dipole moment measurements yielded |μ_a| = 3.48 D and |μ_c| = 2.51 D for the axial form and |μ_a| = 3.85 D and |μ_c| = 1.10 D for the equatorial form. Relative intensity measurements showed the equatorial conformer to be 400 ± 60 cal mole^?1 lower in energy. Several sets of vibrational satellites were observed and natural abundance C¹³ spectra were obtained for the equatorial conformer.     

Microwave spectrum and rotational isomerism of n-propyl isocyanide

The microwave spectrum of n-propyl isocyanide has revealed the existence of two rotational isomers, trans (methyl trans to the isocyanide substituent), and gauche. Plausible structures have been fitted to the data, giving the gauche dihedral angle as 119° ± 2° from the trans position. Stark effect measurements have yielded dipole moments for the two rotamers: μ_trans = 4.16 ± 0.02 D and μ_gauche = 4.10 ± 0.09 D. The rotational constants of the trans form are A = 23 700 ± 100, B = 2407.632 ± 0.020, and C = 2278.853 ± 0.030 MHz, and those of the gauche form are A = 10 208.983 ± 0.030, B = 3479.219 ± 0.015, and C = 2859.981 ± 0.015 MHz. It has been found from relative intensity measurements that the gauche ground state is slightly more stable than the trans ground state, with an energy difference of 99 ± 45 cm^?1. Several vibrationally excited states have been assigned to the torsional motion around the central carbon-carbon bond, the CNC bending motion, and the methyl internal rotation. The torsional vibration frequency is 114 ± 20 cm^?1 in the trans form and 123 ± 20 cm^?1 in the gauche form. A four-term potential function for internal rotation about the central CC bond has been determined.     

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.