C-H and C-D interbond coupling in CHDCl2

Laser photoacoustic spectra of vapour phase CHDCl2 reveal the presence of an interaction which has been ascribed to interbond coupling between C-H and C-D local modes. The absolute value of the interbond coupling parameter for the CHD group, determined from a fit of a model local mode hamiltonian to the experimental data, is shown to be given approximately by the geometric mean of the interbond coupling parameters of the CH2 and CD2 groups recently derived from similar studies of CH2Cl2 and CD2Cl2. Such behaviour is understood in terms of a simple analysis in which kinetic coupling effects dominate. It is suggested that C-H stretch/bend Fermi resonance is responsible for some weaker features in the spectra and modelling calculations are described which allow an order of magnitude estimate of the size of the coupling parameter involved.

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.

Analytical functions for the ground state potential surfaces of C3 (X 1 Σ g+) and HCN (X 1 Σ +)

Analytic functions have been obtained to represent the potential energy surfaces of C3 and HCN in their ground electronic states. These functions closely reproduce the available data on the energy, geometry, and force constants in all stable conformations, as well as data on the various dissociation products, and ab initio calculations of the energy at other conformations. The form of the resulting surfaces are portrayed in various ways and discussed briefly.

Vibration-rotation spectra of 13C containing acetylene: anharmonic resonances

High resolution vibration-rotation spectra of 13C2H2 were recorded in a number of regions from 2000 to 5200 cm−1 at Doppler or pressure limited resolution. In these spectral ranges cold and hot bands involving the bending-stretching combination levels have been analyzed up to high J values. Anharmonic quartic resonances for the combination levels ν1 + mν4 + nν5, ν2 + mν4 + (n + 2) ν5 and ν3 + (m − 1) ν4 + (n + 1) ν5 have been studied, and the l-type resonances within each polyad have been explicitly taken into account in the analysis of the data. The least-squares refinement provides deperturbed values for band origins and rotational constants, obtained by fitting rotation lines only up to J ≈ 20 with root mean square errors of ≈ 0.0003 cm−1. The band origins allowed us to determine a number of the anharmonicity constants xij0.

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.

Calculated rotational and rovibrational spectra of D2S and HDS

Rovibrational energy levels, transition frequencies, and linestrengths are computed variationally for the sulfur hydrides D2S and HDS, using ab initio potential energy and dipole surfaces. Wave-numbers for the pure rotational transitions agree to within 0.2 cm−1 of the experimental lines. For the fundamental vibrational transitions, the band origins for D2S are 860.4, 1900.6, and 1912.0 cm−1 for ν2, ν1, and ν3, respectively, compared with the corresponding experimental values of 855.4, 1896.4, and 1910.2 cm−1. For HDS, we compute ν2 to be 1039.4 cm−1, compared with the experimental value of 1032.7 cm−1. The relative merits of local and normal mode descriptions for the overtone stretching band origins are discussed. Our results confirm the local mode nature of the H2S, D2S, and HDS system.

The fundamental vibration-rotation band of hydrogen chloride

The fundamental vibration-rotational absorption band of hydrogen chloride near 3 45,t has been remeasured using higher resolving power than previously. The wave-lengths of the absorption lines have been determined more precisely, and the isotopic splitting of lines has been completely resolved. The results have provided new and more satisfactory values for the rotational constants Bi, and the centrifugal stretching constants Di, and their relative values for the two isotopic species agree closely with what is to be expected for the difference in mass. The positions of the lines in the pure rotational absorption spectrum have been calculated from the derived data, and agree closely with those recently observed. The bond lengths re for each isotopic species H35C1 and H37C1 is found to be 1-2744A.

Internal rotation in dimethylacetylene

The vibrational spectrum of dimethyl acetylene has been remeasured with better resolving power than hitherto, and the rotational fine structure of some perpendicular type bands has been partly analyzed. The energy levels of a molecule of this kind in which internal rotation of methyl groups may arise have been re-examined theoretically and the rotational structure of the absorption bands has been more clearly defined than previously. The experimental results are consistent with the assumption of unrestricted internal rotation of the methyl groups, and the Coriolis factors $\zeta _{i}$ for several vibrations have been determined.

Intensities in infrared bands V: Bond polar properties in dimethylacetylene

The absolute intensities of all except one of the infra-red fundamental vibration bands of dimethyl acetylene have been determined, and the results have been used to compute polar properties of the C—H and C—C bonds. It has been found that if the very probable assumption is made that the acetylenic carbon atoms carry a residual negative charge, the hydrogen atoms in the C—H bonds must carry a residual positive charge. The probable value of the C—H dipole is about 04 Debye, and that of the C—C bond about 1 Debye. Comparisons have been made with the results of similar work with related molecules.

Vibrational intensities in methane

The absorption intensities of the two infra-red active vibrations in methane have been obtained from a perturbation calculation on the equilibrium wave functions derived in the preceding paper. The perturbation field is the change in the potential field due to the nuclei which results from moving the nuclei in the vibrational coordinate concerned, and a simplified form of second order perturbation theory, developed by Pople and Schofield, is used for the calculation. The main approximation involved is the neglect of f and higher harmonics in the spherical harmonic expansion of the nuclear field. The resulting dipole moment derivatives are approximately three times larger than the experimental values, but they show qualitative features and sign relationships which are significant.

Errors in "Wavefunctions for the methane molecule"

Two errors in my paper “Wave functions for the methane molecule” [1] are corrected. They concern my f-harmonic approximation to the wave-function in the equilibrium configuration, for which the final expression for the wave function, the energy lowering, and the density function were all in error.

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.