The infrared vibration-rotation spectrum of trans and cis nitrous acid

Infrared spectra of the trans and the cis isomers of nitrous acid, both HONO and DONO, have been observed in the gas phase using a Fourier transform interferometer with a resolution of about 0.05 cm−1 from 4000 to 500 cm−1. Rotational analyses are reported on eleven of the fundamentals and some overtones.

Carbon suboxide: the infrared spectrum from 1800 to 2600 cm-1

The infrared spectrum of carbon suboxide has been recorded from 1800 to 2600 cm−1 at a resolution of 0.003 cm−1. About 7% of the ca. 40 000 lines observed have been assigned and analyzed, belonging to 36 different bands. Most of these are associated with the fundamental ν3, at 2289.80 cm−1, and the combination band ν2 + ν4, at 2386.61 cm−1, each of which give rise to a system of sum bands, difference bands, and hot bands involving the low-wave-number fundamental ν7 at 18 cm−1. A few other tentative assignments are made. The bands have been analyzed for vibrational and rotational constants.

The infrared spectrum of silicon difluoride

The infrared spectrum of the stretching fundamentals of SiF2 has been obtained at a resolution of ≈ 0.1 cm−1 using a FTIR spectrometer. The spectrum has been analysed using computer simulation based on a coupled hamiltonian for v1 and v3, giving v1 = 855.01 cm−1 and v3 = 870.40 cm−1. The relative magnitude and sign of the vibrational transition moments has been determined from the ξC13 Coriolis coupling.

Coriolis perturbations in the infrared spectrum of diborane

High‐resolution infrared spectra of B2H6 vapor are reported. The sample was prepared from the naturally occurring 11B☒10B isotopic mixture. The rotational structure of the infrared bands has been analysed for Coriolis perturbations due to rotation about the axis of least moment of inertia (the B⋅⋅⋅B axis). The following results have been obtained: (a) interaction between the Type A fundamental ν18 and the inactive fundamental ν5 has been observed, thus confirming the assignment of ν5 at 833 cm—1, giving ∣ ζ5,18Z ∣=0.55±0.05; (b) interaction observed between the Type A combination band (ν10+ν12) at 1283 cm—1 and the inactive combination (ν10+ν7) gives an estimate of the unobserved fundamental ν7 as 850±30 cm—1, and an estimate of ∣ ζ7,12Z ∣=0.6±0.1; (c) the absence of any observed perturbation of the Type C fundamental ν14 at 973 cm—1, suggests, by negative arguments, that either the unobserved fundamental ν9 does not lie in the frequency range 900 to 1100 cm—1, or ∣ ζ9,14Z ∣<0.2. The assignment of the unobserved fundamental vibrations of diborane is discussed in the light of this evidence.

Anharmonicity and local mode effects in the vibrational spectrum of NiCO4 and Co(CO)3NO

Previously published data on the vibrational fundamentals and overtones of the carbonyl stretching modes of Ni(CO)4 and Co(CO)3NO are reinterpreted using the recent model of Mills and Robiette, including Darling-Dennison resonances and local mode effects. The harmonic wavenumber θm and anharmonicity constant xm associated with the carbonyl and nitrosyl stretching modes are derived, and the 13C and 18O isotopic shifts are discussed in relation to the harmonic and anharmonic force field.

Perturbations in the infrared spectrum of monofluoroacetylene, and their relationship to intramolecular vibrational energy redistribution

Several high-order vibration-rotation perturbations in the high-resolution infrared spectrum of monofluoroacetylene, HCCF, are assigned and analyzed in detail. They result in avoided crossings in the rotational structure of several bands, and precise values for the effective high-order terms in the Hamiltonian have been determined. The significance of these results for intramolecular vibrational redistribution is discussed.

Microwave spectrum of CF3CCH

Attempts to observe ΔK = ±1 transitions in the rotational spectrum of CF3CCH and CF3H in the first excited state of a degenerate vibration, by direct absorption in the Y band and K band regions of the microwave spectrum, have not been successful. In the course of this work the J = 3-2 and 4-3 rotational spectrum of CF3CCH has been observed with higher sensitivity than previously, and from the positions of the vibrational satellites several new rB values have been determined.

Puckering structure in the infrared spectrum of cyclobutane

The theory of rotational-pucker-vibrational transitions in the vibrational spectrum of cyclobutane is reviewed. Puckering sideband structure on the 1453 cm-1v14 infra-red fundamental of C4H8 has been observed and analysed, in terms of two slightly different puckering potential functions for the ground and the excited vibrational states. The results have been fitted to quartic-quadratic potential functions in the puckering coordinate, with a barrier to inversion of 503 cm-1 (1•44 kcal mole-1 = 6•02 kJ mole-1) in the ground state and 491 cm-1 in the excited state ν14 = 1. For reasonable assumptions about the reduced mass, the equilibrium dihedral angle of the C4 ring is determined to be about 35°, in agreement with previous estimates. Ueda and Shimanouchi's observations on the 2878 cm-1 C4H8 band have been re-analysed, and puckering sidebands have also been observed and analysed for the 1083 cm-1v14 infra-red fundamental of C4D8. Pure puckering transitions have been observed in the Raman spectrum of C4H8 vapour. All of these observations are shown to be consistent with the same ground state puckering potential function.

The microwave spectrum of thietan-2,2,4,4-d4

The microwave spectrum for thietan-2,2,4,4-d4 is analysed in six of its lowest puckering states and up to J = 25. The close lying pairs of states of vp = 0/1, 2/3 and 4/5 are treated with a vibration-rotation hamiltonian which includes an off-diagonal coupling term in vp. Additional corrections to this coupling term in higher powers of the angular momentum operator are derived and their importance for improving the fit of calculated to observed data is tested. The variation of the centrifugal distortion constants with vp follows the model of Creswell and Mills (1974, J. molec. Spectrosc., 52, 392). A value is determined for the derivative with respect to the puckering coordinate of the ac-component of the inverse moment of inertia tensor.

Vibrational Renner-Teller effects in the infrared spectrum of carbonsuboxide

The infrared spectrum of carbon suboxide has been recorded with a resolution of 0•01cm-1 from 400 to 700 cm-1. The region from 530 to 570 cm-1 shows intense absorption due to the v6(Πu) band system, of which the fundamental band only has been assigned and analysed, giving v6=540•221 cm-1. The region 590 to 660 cm-1 shows weaker absorption due to the v5(Πg) band system appearing in combination with odd quanta of the v7(Πu) fundamental at 18 cm-1. The v5 + v7 band and several hot bands have been assigned and analysed, and the effective v7 bending potential in the v5 state has been deduced. This potential shows a splitting as the large amplitude bending coordinate q7 is displaced due to interaction between v5 and v7 analogous to the Renner-Teller effect in electronic spectroscopy. This splitting is about 4 cm-1 for the classical turning points in q7 and the mean q7 bending potential is closely similar to that in the ground state.

The infrared spectrum, equilibrium structure and harmonic and anharmonic force field of thioborine, HBS

Infrared spectra of the two stretching fundamentals of both HBS and DBS have been observed, using a continuous flow system through a multiple reflection long path cell at a pressure around 1 Torr and a Nicolet Fourier Transform spectrometer with a resolution of about 0•1 cm-1. The v3 BS stretching fundamental of DBS, near 1140 cm-1, is observed in strong Fermi resonance with the overtone of the bend 2v2. The bending fundamental v2 has not been observed and must be a very weak band. The analysis of the results in conjunction with earlier work gives the equilibrium structure (re(BH) = 1•1698(12) , re(BS) = 1•5978(3) ) and the harmonic and anharmonic force field.

The microwave spectrum of 1-pyrazoline

The microwave spectrum of 1-pyrazoline has been observed from 18 to 40 GHz in the six lowest states of the ring-puckering vibration. It is an a-type spectrum of a near oblate asymmetric top. Each vibrational state has been fitted to a separate effective Hamiltonian, and the vibrational dependence of both the rotational constants and the quartic centrifugal distortion constants has been observed and analyzed. The v = 0 and 1 states have also been analyzed using a coupled Hamiltonian; this gives consistent results, with an improved fit to the high J data. The preferred choice of Durig et al. [J. Chem. Phys. 52, 6096 (1970)] for the ring-puckering potential is confirmed as essentially correct, but the A and B inertial axes are shown to be interchanged from those assumed by Durig et al. in their analysis of the mid-infrared spectrum.

Microwave spectrum of deuterated silyl isocyanate, SiD3NCO

The microwave spectrum of SiD3NCO has been observed and analyzed for 18 different vibrational states in the ν10 manifold. Some accidental resonances have been observed and analyzed. The vibrational dependence of the rotational and l-doubling constant and centrifugal distortion constant DJK has been successfully interpreted in terms of the two-dimensional anharmonic oscillator model.

The high-resolution infrared spectrum of HOF near 2700 cm-1: the ground and 2v2 states

The a/b hybrid-type ν1 fundamental and 2ν2 overtone bands of HOF were investigated by FTIR spectroscopy with a resolution close to 0.008 cm−1. Improved ground state parameters of HOF were determined from a merge of more than 3000 ground state combination differences formed from ν1 and previously measured ν2 transitions with the reported pure rotational lines. Excited state parameters of the v2 = 2 state, ν0 = 2686.924 6(1) and χ22 = −9.942 4(1) cm−1, were determined employing Watson's A-reduced Hamiltonian up to sixth order in I′ representation. The 2ν2 state was found to be unperturbed, the excited state parameters being closely related to those of ν2.

The infrared spectrum of the ν2 and ν3 bands of H16OF, H18OF, and D16OF

Fourier transform IR spectra in the ν2 and ν3 regions between 800 and 1500 cm−1 have been measured of H16OF with a resolution of 0.007 cm−1 and of H18OF and DOF with a resolution of 0.040 cm−1. Ground state constants have been improved for H16OF and have been obtained for the first time for H18OF. Parameters of the v2 = 1 and v3 = 1 excited states have been determined from rovibrational analyses of ca. 1000 ν2/ν3 lines which were fitted with σ 0.36, 4.5, and 7.6 × 10−3 cm−1 for H16OF, H18OF, and D16OF, respectively. Band centers of ν2/ν3 are 1353.40466(5)/889.07974(6), 1350.3976(5)/862.2967(7), and 1002.0083(9)/891.0014(15) cm−1, respectively, for the three isotopic species. While ν2 and ν3 are sufficiently separated in HOF to be treated independently, a Coriolis resonance is evident in DOF, the interaction constant ξ23c = 0.19073(16) cm−1 being in agreement with the prediction from the harmonic force field.