The vibrational spectra of some isotopic species of propionitrile

The infrared and Raman spectra of CH₃CH₂CN, CH₃CD₂CN, and CD₃CH₂CN, and the infrared spectrum of CH₃CH₂¹³CN were investigated in detail between 6000 and 100 cm⁻¹. Some infrared measurements of other isotopic species are also reported and partial assignments given. All fundamentals of propionitrile-d₀, -d₂, -d₃, and -¹³CN were assigned, together with a large number of mainly binary combination bands for which a general method of assignment is given. Several Fermi resonances were detected and the unperturbed positions of some of the levels involved were calculated. Special attention was paid to the CH stretching vibrations for which persisting wrong assignments exist in the literature, and to the methyl torsion frequencies which were determined for the four isotopic species above. A valence force field was calculated, and the potential energy distribution of the normal vibrations is tabulated.     

Matrix isolation study of the infrared spectrum of thioformaldehyde

H₂CS has been trapped in argon and nitrogen matrices at 14 K as a product of the pyrolysis of s-trithiane or (CH₃S)₂ and of the ultraviolet or vacuum ultraviolet photolysis of CH₃SH. A small concentration of H₂CS has also been observed upon vacuum ultraviolet photolysis of a mixture of CH₄ and H₂S in an argon matrix. The isotopic data support the assignment of absorptions at 993 and at 1063 cm^?1 to the out-of-plane deformation and the CS stretching fundamentals of H₂CS. Absorptions in the CH stretching region which were assigned to H₂CS in an earlier gas-phase study were confirmed in the matrix experiments. Studies of the vacuum ultraviolet photolysis of CD₃SH have provided information on the mechanism of the photolysis process.     

Hydrogen-bonded OH and OD overtone bands and potential energy curve of methanol

The absorption spectra of CH₃OH, CH₃OD, CD₃OH, and CD₃OD as pure liquids and as carbon tetrachloride solutions were measured in the 3,850 – 16,600cm^?1 region. In addition to the various combination bands, the higher overtone bands of the hydrogen-bonded OH stretching vibration of self-associated methanols were observed at ～6470, 9300–9700, and 12,200 – 12,700 cm^?1 with broad half-widths of ～700, ～1200, and ～1800 cm^?1, respectively, and those of the OD stretching vibration, at ～4900, 7200–7400, and 9200–9600 cm^?1 with half-widths of ～370, ～700, and ～1200 cm^?1, respectively. With the aid of the observed frequencies, we determined the single minimum potential energy curve for the hydrogen-bonded OH and OD stretching vibrations of self-associated methanols. Furthermore, the absorption band due to double excitation of two neighboring OH groups linked together by a hydrogen bond was quantitatively analyzed by using the isotopic isolation technique. The double excitation band of CH₃OH as pure liquid was found to appear at 6730 cm^?1 with an absorbance of 0.08 at 1 mm light path length.     

Overlapping spectral features and new assignment of 2‐propanol in the C–H stretching region

The vibrational spectra of gaseous and liquid 2‐propanol in the C–H stretching region of 2800 ~ 3100 cm⁻¹ were investigated by polarized photoacoustic Raman spectroscopy and conventional Raman spectroscopy, respectively. Using two deuterated samples, that is, CH₃CDOHCH₃ and CD₃CHOHCD₃, the overlapping spectral features between the CH and CH₃ groups were identified. With the aid of depolarization ratio measurements and density functional theory calculations, a new spectral assignment was presented. In the gas phase, the band at 2884 cm⁻¹ was assigned to the overlapping of one CH₃ Fermi resonance mode and a CH stretching of gauche conformer. The bands at 2917 and 2933 cm⁻¹ were assigned to another two CH₃ Fermi resonance modes, but the latter includes weak contribution from CH stretching of trans conformer. The bands at 2950 and 2983 cm⁻¹ were assigned to CH₃ symmetric and antisymmetric stretching, respectively. The spectral features of liquid 2‐propanol are similar to those in the gas phase except for the blue shift of CH and the red shift of CH₃ band positions, which can be attributed to the intermolecular interaction in the liquid state. The new assignments not only clarify the confusions in previous studies from different spectral methods but also provide the reliable groundwork on spectral application of 2‐propanol in the futures. Copyright © 2014 John Wiley & Sons, Ltd.     

Harmonic Frequencies and Potential Energy Distributions of Partially Deuterated Methyl Cyanide

Although the vibrational spectra and force constants of CH₃CN and CD₃CN have been thoroughly studied, partially deuterated methyl cyanide has received much less attention. The infrared spectrum of CD₂HCN has only recently been reported1 and that of CH2DCN has not yet appeared. Normal coordinate analysis for neither partially deuterated species has appeared. We report here harmonic frequencies and potential energy distributions for both partially deuterated methyl cyanide species, CH₂DCN and CD₂HCN, based on force fields and structural parameters from CH₃CN and CD₃CN. The calculated frequencies for CD₂HCN are compared with the observed infrared frequencies. The vibrational interaction of the relatively high CN stretching frequency and the CD stretching frequencies is also discussed.     

Anharmonic potential function of 1,1-dichloroethylene

A simple anharmonic potential containing 18 quadratic, 6 cubic, and 6 quartic constants is proposed to fit 124 vibrational frequencies of 1,1-dichloroethylene and its ³⁷Cl isotope in the region from 10 000 to 350 cm^?1. The level patterns in the first and the second overtone regions of the CH₂ stretching vibrations are explained by the absence of large higher-order interaction terms between the two CH stretching coordinates.     

Far infrared laser lines produced by methanol and its isotopic species: A review

Methanol (CH₃OH) is considered today one of the most important active media for the generation of laser radiation in the far-infrared (FIR) spectral region. Together with ten of its other isotopic species, it is responsible for the major part of the laser lines generated by the optical pumping technique. Due to the extreme importance of those molecules as laser generators, we understood that there was a necessity of a comprehensive work which would include as much pratical information as possible about each line.Chang et al⁽¹⁾ early recognized methanol as a source of strong FIR laser lines. Since then, more than 100 papers were published containing information about new laser emission. Recently, Moruzzi et al⁽¹¹⁴⁾ presented a review of 575 lines produced by¹²CH₃OH. In the present paper, we have extended the review to the various isotopic modifications of this molecule (namely¹³CH₃OH, CD₃OH,¹³CD₃OH, CD₃OD,¹³CD₃OD, CH₃OD, CH ₃ ¹⁸ OH, CH₂DOH, CH₂DOD and CHD₂OH), a total of nearly 2000 lines with wavelengths ranging from 19µm to 3030µm.     

Uniqueness of methyl fluoride force field

The uniqueness of the general harmonic force field of methyl fluoride is analyzed. The analysis is applicable to other methyl halides as well. Through the compliance scheme, it is seen that by supplementing the data employed by Aldous and Mills (i.e., vibrational frequencies ω_i, Coriolis coupling constants ζ_i and the centrifugal stretching constants D_J, D_JK of CH₃F and CD₃F molecules), with the frequencies of A′ or A″ species of either CH₂DF or CD₂HF, the force field is uniquely determined. The addition of any other extra data including the ¹²CH₃F¹³CH₃F isotopic shifts only makes the determination of the force field parameters more precise.     

High-Resolution Infrared Studies of ν1, 2ν1, and 2ν4 Bands of CHCl3

The C-H stretching fundamental band ν₁ (3033 cm⁻¹) of chloroform CH³⁵Cl₃ has been investigated together with the first overtone 2ν₁ (5941 cm⁻¹) in order to determine the rotation vibration parameters. From the ν₁ band α₁^C=−0.025 46(41)×10⁻³ cm⁻¹ and α₁^B=−0.010 688(44)×10⁻³ cm⁻¹ were obtained. The hot bands connected to the low lying fundamentals ν₃ and ν₆ have been analyzed and anharmonicity constants have been derived. Both the parallel and the perpendicular component band of the C-H bending overtone 2ν₄ have also been studied. In the parallel band (2410 cm⁻¹) more than 900 lines were included in the fit. In the perpendicular band (2443 cm⁻¹) 2615 lines were fitted using a model with one resonance. Among other things the results C₀−C_v=0.025 262 (20)×10⁻³ cm⁻¹, B₀−B_v=0.134 883 (25)×10⁻³ cm⁻¹, and (Cζ)_v=−0.111 867 56 (30) cm⁻¹ were obtained.     

Methanol and deuterated species: Infrared data,valence force field,rotamers, and conformation

New infrared measurements of gaseous and matrix-isolated methanol and 7 deuterated species are presented and analyzed. A revised assignment for the species CH₃OH(D) and CD₃OH(D) is used to determine 15 significant parameters of a valence force field by a converged simultaneous least-squares adjustment to 44 observed fundamentals. The respective frequencies calculated for the rotamers of CH₂DOH(D) and CHD₂OH(D) turn out to be a valid prediction as they are used to assign 78 observed fundamentals of the species with partially deuterated methyl groups. The values of the 15 force constant parameters are refined by including all 122 observed fundamentals. The force field contains significant deviations from local C_3v symmetry of the methyl group. Such an asymmetry, in the CH-stretching diagonal part, produces a difference of about 10 cm^?1 in the zero point energy of symmetric and asymmetric rotamers of the species with partially deuterated methyl groups. Calculations based on equilibrium structures with and without methyl tilt yield better agreement with observed data in the nontilted case. A preliminary calculation of relative intensities reproduces the major effects of isotopic substitution and rotational isomerism. Experimental evidence for the staggered conformation is obtained from a comparison of observed data with calculated results based on staggered and eclipsed models.     

Vibrational spectra of nitromethanes and the effects of internal rotation

Infrared spectra have been obtained in gas and crystalline phases for CH₃NO₂, CD₃NO₂, and CHD₂NO₂. A few Raman liquid measurements have also been made. The crystal spectra show the methyl group to be locked in conformation I,

with isolated CH stretching frequencies 3065 (ν_∥CH) and 3000 (ν_⊥CH), respectively. In the gas phase, the bands due to ν_aCH₃ and ν_aCD₃ are split, the splitting being compatible with isolated frequencies of 3065 (ν_∥CH) and 3006 (ν_⊥CH) cm^?1, respectively. These indicate a variation of 0.006 Å in bond length during internal rotation. The gas phase infrared band at 3028.7 cm^?1 and the Raman liquid band at 3024 cm^?1 in the spectra of CHD₂NO₂ represent averages of the frequencies during internal rotation. All calculations are performed with a potential function involving variations both in diagonal bond stretching, and in off-diagonal stretching interaction constants, proportional to cos2π, where π is the internal rotation angle.In the Appendix, vibrational assignments below 1600 cm^?1 are examined. Product rule considerations and intensity changes upon deuteration lead to a conflict with the infrared gas phase band contour over the assignment of the rCD₃ mode at 884 cm^?1. This and other features in the gas phase spectra may arise from the internal rotation.     

Vibration-rotation spectra and molecular force field of methylene fluoride and methylene fluoride-d2

Infrared spectra of CH₂F₂ and CD₂F₂ have been measured under a medium resolution. The vibration-rotation bands of CD₂F₂ fundamentals have been analyzed and the assignment for the fundamentals of CD₂F₂ is given. In addition, a number of overtone and combination bands are observed for CH₂F₂, which helps to clarify the vibrational assignment for CH₂F₂. A normal coordinate treatment has been carried out: The force constants in a modified Urey-Bradley as well as the general valence force fields have been determined, the vibrational frequencies and the centrifugal distortion constants obtained from microwave spectroscopy being used. The force constants of the methylene fluoride molecule are discussed in connection with those of the related molecules. Special features of the CH₂F₂ and CD₂F₂ spectra are also described.     

Movements of matrix-isolated methyl fluoride and isotopic species studied by infrared absorption spectroscopy

Infrared absorption spectra were recorded in the 10-μm region for the three isotopic methyl fluoride molecules ¹²CH₃F, ¹²CD₃F, ¹³CD₃F, in the four rare gas matrices and in nitrogen. The two lowest fundamental modes ν₃ (CF stretching) and ν₆ (bending) have been systematically studied, as well as the ν₂ and ν₅ modes of ¹²CD₃F. Relative intensity measurements show that the weak ν₆ transition is enhanced by the matrix, compared to its gas-phase value. Frequency measurements yield vibrational shifts which can be compared to a theoretical estimate of the ν₃ shift based on the Lennard-Jones-Devonshire cell model. These molecules are almost freely rotating in the matrices and a rotational analysis in the ν₃ region brings out quantitative values of the barrier to free rotation as defined in Devonshire's theory. Frequency and relative intensity measurements are also reported for dimeric species.     

New spectral assignment of n‐propanol in the C―H stretching region

The C―H stretching vibration serves as an important probe for characterizing molecular structures and properties of hydrocarbons. In this work, we present a detailed study on gas‐phase Raman spectrum of n‐propanol in the C―H stretching region using stimulated photoacoustic Raman spectroscopy. A complete assignment was carried out with the aid of quantum chemistry calculations and depolarization ratio measurement as well as isotope substitutions, i.e. CH₃CD₂CD₂OH, CD₃CH₂CD₂OH and CD₃CD₂CH₂OH. It is shown that the spectra of three C―H groups of n‐propanol overlap each other because of Fermi resonance coupling and different molecular conformations, leading to complex features that were not determined previously. In addition, the comparisons between the spectra of three isotopologues reveal that the C―H vibrations at different sites of carbon chain exhibit different sensitivity to conformational change of n‐propanol. The CH₃ stretching vibration at terminated γ‐carbon is not sensitive whereas the CH₂ stretching vibrations at both α‐carbon and β‐carbon atoms are sensitive. Furthermore, Raman spectra of liquid propanol recorded by conventional spontaneous Raman technique are reassigned on the basis of gas‐phase analysis. Copyright © 2016 John Wiley & Sons, Ltd.     

The harmonic force fields of methylene chloride and dichlorosilane from combined microwave and infrared data

The harmonic force fields of methylene chloride and dichlorosilane have been obtained by combining the vibrational wavenumbers and centrifugal distortion constants of several isotopic species. Although enough data were available from earlier work for dichlorosilane, it was first necessary for methylene chloride to determine its distortion constants from microwave spectra. Transitions were measured up to J = 80 and J = 90 for CH₂Cl₂ and CD₂Cl₂, respectively, and the analysis gave accurate rotational constants, and quartic and sextic distortion constants. Ground-state effective, substitution, ground-state average and approximate equilibrium structures have been obtained for both molecules.     

Spectra and structure of organogermanes: Microwave and Raman spectra of methyltrichlorogermane

The microwave spectrum of methyltrichlorogermane has been investigated in the region 26.5 to 40.0 GHz. The ground state rotational constants, B, were found to be 1602.19, 1601.42, 1601.10, 1600.71, 1600.02, 1537.84, 1537.10, and 1536.36 MHz for the symmetric top molecules CH₃⁷⁰Ge³⁵Cl₃, CH₃⁷²Ge³⁵Cl₃, CH₃⁷³Ge³⁵Cl₃, CH₃⁷⁴Ge³⁵Cl₃, CH₃⁷⁶Ge³⁵Cl₃, CH₃⁷⁰Ge³⁷Cl₃, CH₃⁷²Ge³⁷Cl₃, and CH₃⁷⁴Ge³⁷Cl₃, respectively. For the asymmetric top molecules CH₃⁷²Ge³⁵Cl₂³⁷Cl and CH₃⁷⁴Ge³⁵Cl₂³⁷Cl the ground state rotational constants A, B, and C were found to be 1597.96, 1559.31, 1203 and 1597.17, 1558.59, 1207 MHz, respectively. From the rotational constants the r_s values for the GeCl bond distance of 2.135 ± 0.006 Å and the CGeCl bond angle of 106.0 ± 0.7° were obtained. The centrifugal distortion constant for the CH₃Ge³⁵Cl₃ species was calculated to be 0.35 ± 0.08 kHz. The Raman spectra of methyltrichlorogermane has been recorded in the gas phase and the methyl torsional overtone (Δν = 2) was observed. From the observed frequency shift the barrier to internal rotation has been calculated to be 1.45 kcal/mole.     

Microwave spectrum and conformation of thiomorpholine

The microwave spectrum of normal thiomorpholine (CH₂CH₂SCH₂CH₂NH) was investigated within the region 8–40 GHz, and that of N-deuterothiomorpholine (CH₂CH₂SCH₂CH₂ND) within the region 26.5–40 GHz. The observed spectra are due to the chair equatorial conformers. The rotational constants of both isotopic species were determined for the ground states and for two vibrationally excited states. The dipole moment components and quadrupole coupling constants of normal thiomorpholine and the iminohydrogen r_s coordinates were also determined.     

Infrared spectrum and molecular force field of CF2Cl2

The infrared spectrum of CF₂Cl₂ has been measured under medium resolution in the range 1600-400 cm^?1. More than 100 bands including fundamental, overtone, combination, and “hot” bands of the three isotopic species CF₂³⁵Cl₂, CF₂³⁵Cl³⁷Cl, and CF₂³⁷Cl₂ have been identified. The band contour studies have enabled the fundamental vibrations to be unambiguously assigned, including the modes ν₃ and ν₇, the positions of which were previously in doubt. The observed values for CF₂³⁵Cl₂ in conjunction with the frequency shift data for CF₂³⁵Cl³⁷Cl and CF₂³⁷Cl₂ have been used in determining a general valence force field, which adequately describes the system investigated. A Fermi resonance interaction between ν₈ and ν₃ + ν₉ levels for the three isotopic species has been interpreted. The corresponding perturbations between those levels obtained by adding ν₂ or ν₅ to both ν₈ and ν₃ + ν₉ have also been found and the related features carefully investigated.     

Near-infrared spectra of hydrogen-bonded cyclic dimers of some carboxylic acids

Near-infrared spectra in the 3900–11000 cm⁻¹ region were measured for formic and acetic acids and also for their deutero analogs in the gaseous state at various temperatures. Observed monomer and dimer bands were assigned to overtone and summation bands of various vibrational modes. Special attention was paid to the first overtone bands of the OH and OD stretching modes of the hydrogen-bonded cyclic dimers, which were observed at ∼5930 cm⁻¹ and ∼5870 cm⁻¹ for formic-d acid and acetic-d₃ acid, respectively, and also at ∼4370 cm⁻¹ for acetic acid-d. On the basis of these data the anharmonicity constants were calculated for the OH and OD stretching modes and were found to increase by hydrogen-bond formation in the gaseous state. Hydrogen-bonded overtone bands are broad and have submaxima with intervals nearly half of those of the OH and OD fundamental bands. The results concerning the band breadths of the OH and OD stretching vibrations of the dimers were interpreted on the line of the idea that they strongly couple with the O?O stretching vibration.