Anharmonic force field for FCP

It is shown that, whereas a simple harmonic force field suggests that the FC stretching constant exceeds that for CP, a fuller anharmonic treatment suggests values of 806 and 946 N m^?1, respectively. Equilibrium bond lengths are 127.17 and 154.81 pm respectively.     

The microwave spectrum of C-fluorophosphaethyne FCP: Structure determination,dipole moment,and vibration-rotation data

The microwave spectrum of the new linear triatomic molecule C-fluorophosphaethyne FCP which is produced when CF₃PH₂ vapor passes over solid KOH at room temperature and ca. 20 μmHg pressure has been studied. Transitions belonging to the two isotopic variants ¹⁹F¹²C³¹P and ¹⁹F¹³C³¹P have been analyzed and the resulting structural data are $\text{r(}\text{FC}\text{) = 1.285 ± 0.005}\text{A}\text{?}$ and $\text{r(}\text{CP}\text{) = 1.541 ± 0.005}\text{A}\text{?}$. The study has yielded the following spectroscopic parameters for ¹⁹F¹²C³¹P: B₀ = 5257.80 ± 0.03 MHz, α₂ = ?11.95 ± 0.05 MHz, q₂ = 4.478 ± 0.002 MHz, and μ = 0.279 ± 0.001 Debye.     

The microwave spectrum,harmonic force field,and structure of difluorodichloromethane

Very large numbers of rotational transitions have been accurately measured for ¹²CF₂³⁵Cl₂, ¹²CF₂³⁵Cl³⁷Cl, and ¹³CF₂³⁵Cl₂, and have been analyzed for rotational constants and quartic centrifugal distortion constants. The distortion constants have been combined with vibrational wavenumbers (both from the literature and from the present work), and with ab initio force constants also evaluated in the present work, to give an approximate harmonic force field. The rotational constants and force field have been used to evaluate ground state effective, substitution, and ground state average structures for the molecule.     

The microwave spectrum,harmonic force field,and structure of formyl chloride

Extensive measurements were made of the microwave spectra of nine isotopic species of formyl chloride, HCOCl. Analysis of these spectra gave accurate rotational constants, chlorine nuclear quadrupole coupling constants, and centrifugal distortion constants. The distortion constants, together with the vibrational wavenumbers, were used to evaluate a valence harmonic force field. Effective, substitution, ground-state average, and estimated equilibrium structures are presented.     

The harmonic force field of methanol

A 28-parameter harmonic force field for methanol is calculated from the matrix frequencies and frequency shifts of ten isotopic species of methanol determined by Barnes and Hallam; Mallinson and McKean; and Serrallach, Meyer, and Günthard. This present force field reproduces the observed harmonic frequencies and frequency shifts far better than either of the two most recent force fields. The presence of a 20 cm^?1 Fermi resonance shift on the lower A′ CH₃ stretching mode deduced in an earlier work is confirmed here.     

The microwave spectrum,harmonic force field,and structure of carbonyl chlorofluoride,OCCIF

Rotational spectra of three isotopic species of carbonyl chlorofluoride, OCCIF, have been extensively measured, and have been analyzed for rotational constants, quartic centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants. Ab initio calculations of the harmonic force field have been made using several different sets of basis functions, and their relative cost efficiency has been assessed. The measured distortion constants have been combined with vibrational wavenumbers (both from the literature and from the present work) and with the ab initio force constants to refine the force field. Ground state effective (r₀) and average (r_z) structures have been evaluated for the molecule.     

The general harmonic force field of fluoroform

Anharmonicity constants and harmonic frequencies of HC¹²F₃ and DC¹²F₃ are obtained for the first time. These data are combined with ζ^z, ζ^x,y and centrifugal distortion constants and carbon-13 frequency shifts to obtain, using the display method, the general harmonic force field (GHFF) of fluoroform. All 12 force constants in the GHFF, including off-diagonal elements in the A₁ block, are determined with significance. The carbon-13 frequency shifts proved to be most important for precise determination of A₁ off-diagonal elements. The GHFF is compared with the predictions of the Hybrid Orbital Force Field (HOFF).     

The microwave spectrum,harmonic force field,and ground state average structure of 1,1-dichloroethylene

The microwave spectra of several isotopic species of 1,1-dichloroethylene have been measured up to high J values and have been analyzed for rotational constants and quartic centrifugal distortion constants. An approximate harmonic force field for the molecule has been obtained by combining the centrifugal distortion constants with known vibrational data. The harmonic force field has been used together with the results of the present and other microwave studies to determine the ground state average molecular structure.     

The harmonic force field and structure of chloryl fluoride

The microwave spectra of three isotopic species of chloryl fluoride, FClO₂, previously published by Parent and Gerry (J. Mol. Spectrosc., 49, 343–364 (1974)), have been refit to rotational constants and centrifugal distortion constants using Watson's Hamiltonian in both its A and S reductions. The quartic distortion constants have been combined with the vibrational data of Smith, Begun, and Fletcher (Spectrochim. Acta, 20, 1763–1770 (1964)) to calculate a refined harmonic force field. The rotational constants and force field have been used to calculate a zero-point average structure and an approximate equilibrium structure. Both the force field and structures are in essential agreement with those published earlier.     

The emprical general harmonic force field of ethane

A total of 175 spectroscopic data, accumulated from 10 isotopic species of ethane, are used to define all 22 parameters of the harmonic potential function within narrow limits. Before calculation, numerous Fermi resonances have been identified and quantified through infrared and Raman spectroscopic studies of CH₃CD₃ and its ¹³C isotopic species. This is an essential prerequisite to such an investigation, without which a self-consistent empirical data set cannot be achieved from which to determine physically meaningful force constants. Comparison of the empirical force constants with those predicted by scaled ab initio calculations shows an excellent degree of correspondence in all force constants, and confirms that both approaches can lead to essentially identical results. Calculated values of spectroscopic data of reliable quality are listed. These should be of value to future spectroscopic investigation of isotopic ethanes and for resolving the many resonance perturbations which are present.     

The infra-red spectrum of 13CH3F and the general harmonic force field of methyl fluoride

Analyses of the v ₃, 2v ₃, and (predominantly) v ₁ parallel bands, and of the v ₄ and v ₆ perpendicular fundamentals have been made for ¹³CH₃F in terms of the rotational structure observed with a resolution of ～0·2 cm^-1. In addition, the band centres of the strongly Coriolis-interacting v ₂ and v ₅ fundamentals are accurately located. Some elucidation of the complex Fermi resonance interactions in the 3000 cm^-1 region is achieved through study of spectra of crystalline samples. This enables all three components of the v ₁, 2v ₂, 2v ₅ ⁰ triad to be observed for both ¹²CH₃F and ¹³CH₃F, and estimates to be made for the unperturbed vibration frequencies.

The ¹³C frequency shifts determined for all six fundamentals are used in conjunction with existing frequency, Coriolis ζ, and centrifugal distortion data for CH₃F, CD₃F, CHD₂F and CH₂DF, to determine the general harmonic force field for methyl fluoride. The extra shift data enable all 12 parameters of the force field to be fixed within narrow limits for the first time. The disagreement with predictions of the hybrid orbital model in the A₁ species can be attributed to the effect of trans repulsions arising from the fluorine lone-pair electrons, an effect which contributes to the longer CH bond in methyl fluoride compared with the other methyl halides.     

Fermi resonance in the spectrum of deuterated monofluoroacetylene

A strong Fermi resonance interaction between two Σ-type levels ν₂ and 2ν₃ of DCCF together with the corresponding resonance between the levels ν₂ + ν₃ and 3ν₃ has been observed. The rotational structure of the bands has been investigated in both the diads which are situated around 2100 and 3100 cm^?1. The molecular constants involved have been derived.     

The harmonic inversion of the field-swept fixed-frequency resonance spectrum

When the spin Hamiltonian is a linear function of the magnetic field intensity the resonance fields can be determined, in principle, by an eigenfield equation. In this report, we show a new technical approach to the resonance field problem where the eigenfield equation leads to a dynamic equation or, more specifically, to a first order differential equation of a variable L(x), where x is associated with the magnetic field h. Such differential equation has the property that: its stationary solution is the eigenfield equation and the spectral information contained in L(x) is directly related to the resonance spectrum. Such procedure, known as the "harmonic inversion problem" (HIP), can be solved by the "filter diagonalization method" (FDM) providing sufficient precision and resolution for the spectral analysis of the dynamic signals. Some examples are shown where the resonance fields are precisely determined in a single procedure, without the need to solve eigenvalue equations.     

The harmonic force field and ground-state average structure of difluoroborane

An improved harmonic force field of difluoroborane has been calculated using the vibrational wavenumbers and quartic centrifugal distortion constants of four isotopic species. The unidentified vibrational mode ν₅ is predicted at 1049 ± 50 and 775 ± 50 cm⁻¹ for HBF₂ and DBF₂, respectively. The ground-state average structure of HBF₂ has been found to be r_z(BH) = 1.195 ± 0.003 Å; r_z(BF) = 1.315 ± 0.001 Å; (FBF) = 118.0 ± 0.1°.     

The harmonic force field and ground-state average structure of allene

Existing spectroscopic data for allene-H₄, -D₄, and -1,1-D₂ are improved and augmented by gas-phase Raman and solid-phase infrared studies. A number of ¹³C vibration frequencies are identified in natural abundance by each technique. A total of 58 input data enable 22 of the 23 force field parameters to be determined, the ¹³C frequency shift data removing the ambiguity of choice between two sets of A₁ and B₂ species force constants. The remaining interaction force constant is constrained to the predicted ab initio value of Botschwina and Pulay. The force field is used to determine the ground-state average (r_z) structure of allene. Observed trends in the H-D isotopic effects on the r_z structures of ethylene, allene, and ketene are in accordance with those expected.     

Fourier transform emission spectroscopy: The vibration-rotation spectrum of CuH

The Fourier transform infrared emission spectrum of CuH was observed. The (1, 0), (2, 1), and (2, 0) vibration-rotation bands of both ⁶³CuH and ⁶⁵CuH were recorded from a copper hollow-cathode discharge in neon and hydrogen. Improved molecular constants for the v = 0, 1, and 2 levels of CuH are provided. This work is the first observation of a vibration-rotation spectrum of a metal hydride in emission.     

Vibration-rotation spectra and the harmonic force field of HOCl

Vibration-rotation spectra of HOCl have been measured at a resolution of 0.05 cm^?1 to determine vibration rotation constants, and 35–37 Cl isotope shifts in the vibration frequencies. The spectrum of DOCl has also been recorded, and a preliminary analysis for the band origins has been made. The vibrational frequency data and centrifugal distortion constants have been used to determine the harmonic force field in a least-squares refinement; the force field obtained also gives a good fit to data on the vibrational contributions to the inertial defect. The equilibrium rotational constants of HOCl have been obtained, and an equilibrium structure has been estimated.     

Evolution of charged grains in harmonic force field

Evolution of the spatial structure of the massive charged grains in the presence of weak linearly space-dependent external force in a dusty plasma is studied using molecular dynamics simulation. The interaction among the dust grains in the background electron-ion plasma is described by a modified Yukawa interaction potential that includes both repulsive and attractive ranges. Evolution of the initially homogeneously distributed dust grains is followed until a quasi-stationary state is reached. Even though the external force is radially highly asymmetric, the final configuration of the charged grains can be a circular crystal. Still driven by the external force, the grains in the crystal execute synchronized oscillations in the direction of the force. The time needed to reach the quasi-stationary state decreases with increase of the strength of the external force.