F. Scappini

Infrared spectroscopy of carbo-ions. VI: C-H stretching vibration of the acetylene ion C2H2+ and isotopic species

The infrared spectra of the band of the 2Π–2Π asymmetric hydrogen stretching vibration in the three isotopic acetylene ions C2H2+ (ν3), 13C2H2+ (ν3), and DCCH+ (ν1) have been observed and analyzed. The high resolution infrared spectra were recorded using a difference‐frequency laser spectrometer as the tunable coherent infrared source probing an ac glow discharge. Velocity modulation, noise subtraction, and unidirectional multipassing of the infrared beam through the discharge cell provided high sensitivity. C2H2+ was produced in a gas mixture of H2, He, and either CH4 or C2H2, with a total pressure of ≊7 Torr in multiple‐inlet–outlet air‐, water‐, and liquid‐nitrogen‐cooled discharge tubes; C2H2 freezing precluded its use in liquid‐N2‐cooled discharges. Complicated by a strong perturbation whose maximum occurred at N’=15 for F1 and N’=14 for F2, the assignment of the spectrum of normal C2H2+ was made possible by (1) fortuitous discharge conditions which provided unambiguous discrimination of C2H2+ lines ...

Microwave investigation of lactonitrile. Potential functions to the hydroxyl and methyl group torsions

The rotational spectrum of lactonitrile, CH3CH(OH)CN, has been reinvestigated. The analysis has been extended to the CH3CH(OD)CN species and to several excited states of the hydroxyl and methyl internal rotations. The molecule exhibits two conformers with the hydroxyl hydrogen gauche with respect to the cyano group. The conformer A with the hydroxyl hydrogen adjacent to the methinic hydrogen is 118±30 cm−1 (75±30 cm−1 for the OD species) more stable than the conformer B with the hydroxyl hydrogen adjacent to the methyl group. The barrier height to the interconversion is about 400 cm−1. Rotational A–E splittings due to methyl internal rotation have been observed in the first excited state of both conformers, yielding effective V3 barriers of 3.7 kcal/mol for conformer A and 4.3 kcal/mol for conformer B. By using a one‐dimensional flexible model treatment the potential function and the structural relaxation associated with the OH torsion have been determined from the level spacings and the variations of the...

Microwave spectrum of axial cyclohexyl chloride and conformational equilibrium in cyclohexyl chloride

Abstract The high-resolution microwave spectrum of the axial conformer of cyclohexyl chloride has been assigned for both the Cl(35) and Cl(37) isotopic species, in natural abundance. Moreover, the high-resolution microwave spectrum of the equatorial conformer, previously assigned in the ground state [ Chem. Phys. Lett. 21 , 592–594 (1973)], has been further investigated. Several low-energy vibrational satellites have been studied for the Cl(35) isotopic species of both the axial and the equatorial isomers. The ground state centrifugal distortion constants for both the isotopic species of the two rotamers, and the quadrupole coupling constants of Cl(35) and Cl(37) axial isomer and of Cl(37) equatorial isomer (not reported previously) have been determined. From line relative intensity measurements the energy difference between the two conformers has been calculated to be 0.51 ± 0.15 kcal/mol, the equatorial isomer being more stable. In the same way, the vibrational energies of the investigated vibrational satellites have been computed. A structural model for axial cyclohexyl chloride is proposed on the basis of the available experimental data.

Hyperfine structure analysis of stibine in the ground and in the v4 = 1 states

Abstract The two isotopic forms of stibine, 121 SbH 3 and 123 SbH 3 , have been spectroscopically studied with high resolution. Pure quadrupole resonances both in the ground and in the v 4 = 1 states have been observed using the infrared-radiofrequency double resonance technique in a CO 2 laser cavity. Characteristic hyperfine patterns resulting from direct l -type doubling transitions in the v 4 = 1 state have been measured by microwave spectroscopy. The hyperfine pattern in the ground state is reproduced following the standard treatment. Strong vibration-rotation interactions between the v 2 = 1 and v 4 = 1 states affect the observed spectrum in the v 4 = 1 state. A refined treatment of the vibration-rotation interactions between the hyperfine levels in this state was necessary in order to adequately analyze the experimental data. Quadrupole interaction parameters for a degenerate state of a symmetric-top molecule have been determined for the first time.

High-resolution microwave spectrum of cyclohexyl bromide

Abstract The high-resolution microwave spectra of the79Br and81Br isotopic species of cyclohexyl bromide, C6H11Br, have been assigned for the equatorial and axial isomers, respectively. The ground-state energy of the axial isomer is 0.72 ± 0.30 kcal/mole higher than that of the equatorial one. The quadrupole coupling constants have been obtained for the equatorial and axial ground states of both the isotopes. Several vibrational excited states of the equatorial and axial conformers (79Br) have also been analyzed.

Direct I-type doubling transitions in the v4 = 1 state of PH3

Abstract The first three direct I-type doubling transitions in the v4 = 1 state of PH3 have been measured. The I-type doubling constant q4 has been evaluated to be 5267.10(60) MHz.

Determination of the electric dipole moment by microwave spectroscopy in complicated cases using different methods

Abstract Three methods are discussed to determine the electric dipole moment of asymmetric top molecules in those cases where the conventional second order Stark pattern is difficult to identify, because of spectral complexity. The methods are applied to a test molecule and to a number of molecules whose dipole moments were not previously determined.

Infrared-radiofrequency double resonance spectroscopy of CH3F using a color center laser

Abstract A tunable color center laser has been used as the infrared radiation source for infrared-radio-frequency double resonance spectroscopy. The A1–A2 splitting (J, K = 1, l = 1 and J, K = 2, l = −1) in the ν4 vibrational state of CH3F has been studied. This technique has also been used to measure the electric dipole moment for the ν4 state, which has been determined to be 1.8332(23) D.

Vibrationally induced nuclear quadrupole coupling in the v3=1 state of 189OsO4

Electric nuclear quadrupole hyperfine structure arising from a quadrupolar nucleus at the center of tetrahedral molecules, such as 189OsO4, is symmetry forbidden. However, through vibration–rotation distortion a small nuclear quadrupole coupling is induced. The hyperfine structure due to the vibrationally induced eqQ has been measured for a number of P‐ and R‐branch transitions in the ν3 fundamental of 189OsO4, by using inverse Lamb dip spectroscopy. Microwave modulation sidebands of CO2 laser lines have been used as the tunable infrared radiation. From the analysis of the observed hyperfine structure patterns, the values of the scalar and tensor coupling constants have been determined to be χVs=−4.103±0.048 MHz and χVt=−3.090±0.059 MHz.

Extended measurements of the millimeter wave spectrum of H2COH

Abstract Thirteen ground state rotational lines of protonated formaldehyde, H 2 COH + , were measured using a magnetically confined negative glow discharge as a production source. These new measurements together with those of Chomiak et al. [Can. J. Phys. 72 (1994) 1078] have allowed a refinement of the rotational parameters. The astrophysical aspects of previous and future searches of this ion are outlined.