Microwave spectrum of CHD2CN and CHD2NC,and the harmonic force field and rz structure of methyl cyanide and isocyanide

The microwave spectra of CHD₂CN and CHD₂NC have been measured from 18 to 40 GHz; about 20 type A and 30 type C transitions have been observed for each molecule. These have been fitted to a Hamiltonian using 3 rotational constants, and 5 quartic and 4 sextic distortion constants, in the I^rS reduction of Watson [in “Vibrational spectra and structure” Vol. 6 (1977)]; the standard error of the fit is 26 kHz. For methyl cyanide the 5 quartic distortion constants have been used to further refine the recent harmonic force field of Duncan et al. [J. Mol. Spectrosc.69, 123 (1978)], but the changes are small. Finally, for both molecules, the harmonic force field has been used to determine zero point average moments of inertia I_z from the ground state rotational constants for many isotopic species, and these have been used to determine an r_z structure. The results are compared with r_s structure calculations.     

Microwave spectra of deuterated arsines: Distortion moment transitions of AsD3, microwave spectra of AsH2D and AsHD2, and the structure of arsine

Microwave spectra of three deuterated arsines have been measured and analysed. For AsD₃ distortion moment transitions have been observed for the first time, in the form of the K = ±1 ← ∓2 cluster; their frequencies have been combined with those of previously observed “normal” transitions to give rotational, centrifugal distortion, and ⁷⁵As hyperfine constants. For AsH₂D and AsHD₂, the measurements have been extended considerably and now include for the first time R-branch transitions; similar spectroscopic constants have been evaluated. The data have been combined with earlier results for AsH₃ and with vibrational data in a harmonic force field analysis. Both ground state average (r_z) and equilbbrium (r_e) structures have been estimated.     

Comparison of empirical and ab initio force fields for phosphine

Existing experimental data on frequencies, Coriolis coupling constants, and centrifugal distortion constants for phosphine can be reconciled by means of a harmonic force field, provided substantial vibrational dependences of the distortion constants are permitted. Such dependences are indicated in a recent high-resolution study of PD₃. The resulting empirical force constants are then in excellent agreement with existing predicted values from a sophisticated ab initio study, including electron correlation.     

Centrifugal distortion effects in SF2: Calculation of the force field and infrared spectrum

Measurements of the microwave spectrum of SF₂ have been extended up to J = 43 in order to account for the effects of centrifugal distortion. Seventy-five transitions have been included in a weighted least squares fit of the measured spectrum with an rms deviation of 0.078 MHz. The force field for SF₂ has been determined from the centrigufal distortion constants. The vibrational spectrum, as yet unobserved, has been predicted from the force field as have been the Coriolis coupling constants and the average structure.     

The microwave spectrum and structure of chloryl fluoride

The microwave spectra of three isotopic species of chloryl fluoride, FClO₂, in its ground vibrational state, have been measured in the frequency region 8–37 GHz. The spectra have yielded values for the rotational constants, centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants, as well as the molecular dipole moment, 1.722 ± 0.03 D. The molecule has been shown to have C_s symmetry, and a pyramidal configuration, with the chlorine atom at the apex of the pyramid. The following internuclear parameters were obtained:r(Cl?F)1.697±0.003 A r(Cl?F)=1.418±0.002AThe structural parameters, quadrupole coupling constants, dipole moment and force field are explained in terms of a bonding scheme in which a fluorine 2p atomic orbital overlaps with the highest occupied orbital of ClO₂; there is considerable evidence for withdrawal of electron density from this singly occupied antibonding orbital of ClO₂ toward the fluorine atom.     

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 force field and rz structure of Ketene

Recently determined Coriolis coupling constants for H₂ and D₂ Ketene, centrifugal distortion constants for H₂, HD, and D₂ Ketene have enabled 16 of the 19 parameters in the general force field of Ketene to be determined with significance, the ambiguity between the choice of two sets of A₁ and B₁ species force constants being removed. The r₀ structure has been redetermined using the latest values of the rotational constants of H₂, HD, and D₂ Ketene and an r_z structure has been determined for the first time.     

The microwave spectrum, structure, chlorine nuclear quadrupole coupling constants, dipole moment, and centrifugal distortion constants of dichlorosilane

The microwave spectra of three isotopic species of dichlorosilane, SiH₂Cl₂, in its ground vibrational state, have been measured in the frequency region 8–40 GHz. The spectra have yielded values for the rotational constants, centrifugal distortion constants, and chlorine nuclear quadrupole coupling constants, as well as the molecular dipole moment, 1.13 ± 0.02 D. The molecule has C_2v symmetry, and the bond lengths and angles r(Si---Cl=2.033±Å, r(Si---H)=1.480±0.015Å, (Cl---Si---Cl)=109°43′±20±, (H---Si---H)=111°18′±40′ The centrifugal distortion constants have been compared with those calculated using a published force field.     

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.     

Equilibrium structure of protonated cyanogen, HNCCN

The cubic force field of protonated cyanogen, HNCCN⁺, has been calculated at the CCSD(T) level of theory employing correlation consistent bases of quadruple-zeta quality. Semi-experimental equilibrium structures have then been derived from the experimental ground-state rotational constants available for various isotopologues and the corresponding vibrational corrections calculated from the theoretical force fields. While a good agreement has been found with the pure theoretical best estimate of equilibrium geometry, computed at the CCSD(T) level of theory accounting for basis set truncation as well as including core correlation corrections, large discrepancies have been noted with the experimental substitution, r_s, as well as effective, r₀, structures.     

Rotational spectrum and structure of asymmetric dinitrogen trioxide, N2O3

The rotational spectra of the ground vibrational state and the ν₉ = 1 torsional state have been reinvestigated and accurate spectroscopic constants have been determined. The torsional frequency, ν₉ = 70(15) cm⁻¹, has been determined by relative intensity measurements. The assignment of the infrared spectrum has been slightly revised and an accurate harmonic force field has been calculated. The equilibrium structure has been determined using different, complementary methods: experimental, semi-experimental and ab initio, leading to r(NN) = 1.870(2) Å, in particular.     

Ground-state constants, ab initio anharmonic force field, and equilibrium structure of F2BOH

The millimeterwave spectra of F₂¹⁰BOH and F₂¹¹BOH (difluorohydroxyborane) have been measured in their ground vibrational state. Accurate rotational and centrifugal distortion constants have been determined. The equilibrium geometry and anharmonic force fields have been calculated at the CCSD(T) level of theory. The ab initio centrifugal distortion constants and rotation-vibration interaction constants are compared to the experimental values. Some discrepancies are found and discussed. Particularly, it is explained why the semi-experimental structure is not reliable. The best equilibrium structure is: r_e(BF_cis) = 132.29 pm, r_e(BF_trans) = 131.29 pm, r_e(BO) = 134.48 pm, r_e(OH) = 95.74 pm, ∠_e(FBF) = 118.36°, ∠_e(F_cisBO) = 122.25°, and ∠_e(BOH) = 113.14°.     

The pure rotational spectra of the lanthanum monohalides, LaF, LaCl, LaBr, LaI

Pure rotational spectra have been measured for all the major isotopomers of the lanthanum monohalides, LaF, LaCl, LaBr, and LaI, in their ground and (except for ) excited vibrational states. The spectra were observed with a cavity pulsed jet Fourier transform microwave spectrometer in the frequency range 5-24 GHz. The molecules were prepared by laser ablation of La metal and allowing the resulting plasma to react with SF₆, Cl₂, Br₂, or CH₃I precursor in an Ar carrier gas of the pulsed jet. For LaBr this is the first reported spectrum of any kind. Rotational constants, centrifugal distortion constants, nuclear quadrupole coupling constants, and nuclear spin-rotation constants have been determined for all the molecules. Accurate equilibrium (r_e) internuclear distances have given an indication of where the Born-Oppenheimer approximation is beginning to fail. From the centrifugal distortion constants and vibration-rotation (α_e) constants good estimates of the harmonic vibration frequencies and bond dissociation energies have been obtained. The halogen nuclear quadrupole coupling constants indicate the molecules to be highly ionic.     

The Equilibrium Structure of Silyl Fluoride

The experimental equilibrium structure of silyl fluoride has been determined using new sets of accurate rotational constants that have recently been obtained by taking into account the most important interactions between the excited vibrational states. The equilibrium structure has also been calculated at the CCSD(T) level of theory with the cc-pVQZ+1 basis set (including corrections for the core correlation). The anharmonic force field up to semidiagonal quartic terms has been calculated at the MP2 level of theory and the equilibrium structure has been derived from the experimental rotational constants and the ab initio rovibrational interaction parameters. Finally, the average structure of both ²⁸SiH₃F and ²⁸SiD₃F has been reevaluated and used to derive the equilibrium structure. These structures are compared and the experimental structure is found to be in slight disagreement with the other ones. The preferred structure is obtained by calculating the median value of the different structures. The results are r_e(SiF)=1.5907 (9) Å, r_e(SiH)=1.4696 (13) Å, ∠_e(HSiF)=108.32(15)°, and ∠_e(HSiH)=110.60(14)°.     

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 microwave spectrum,force field and dipole moment of CF2

Measurements of the microwave spectrum of CF₂ have been extended to include transitions up to J = 40. Using these extended measurements, a centrifugal distortion analysis has been performed and from the distortion constants, the force field, infrared spectrum, average structure, Coriolis coupling constants, and inertial defect have been calculated. The original assignment of the infrared spectrum has been confirmed. An improved value for the dipole moment, 0.469 ± 0.026 D, has been obtained.     

The harmonic force field and rz structure of HNCO

The presently available microwave, millimeter wave, and far-infrared data of five isotopic species of isocyanic acid, namely, HNCO, H¹⁵NCO, HN¹³CO, HNC¹⁸O, and DNCO, have been used to obtain improved values of the ground-state rotational constants, the five quartic distortion constants, and some higher-order distortion constants in the I^rS reduced Hamiltonian of Watson. The appropriate planarity relation among the quartic centrifugal distortion constants has been imposed in the fitting procedure. The general harmonic force field of isocyanic acid has been determined using all existing data, and assuming a trans bent equilibrium geometry of the molecule with an NCO angle of 170°. Finally an r_z structure has been obtained using the A_z, B_z, and C_z rotational constants of five isotopic species. The bending of the NCO chain is found to be 8° in the trans configuration.     

Microwave spectra of HPO and DPO: molecular structure

Microwave spectra of the unstable phosphorus containing molecule, HPO, and its deuterated species were measured in the frequency range of 70-380 GHz. The molecule was produced by a DC-glow discharge of a gas mixture of PH₃, CO₂, and H₂(D₂). Rotational constants and centrifugal distortion constants for HPO and DPO were determined accurately. Harmonic force constants were evaluated from the centrifugal distortion constants determined in the present study, and with vibrational frequencies reported previously. The zero-point average structure for HPO was obtained by taking the isotopic difference of the PH bond length into consideration: r_z(PH)=1.473(7) Å, r_z(PO)=1.4843(9) Å, and θ_z=104.57(16)°. The errors were estimated from the residual inertial defect. Equilibrium bond lengths for the PH and PO bonds were derived as 1.455(7) and 1.4800(9) Å, respectively, by assuming anharmonic constants of the corresponding diatomic molecules.     

The millimeter wave spectrum of phosphorus oxychloride

Millimeter wave rotational spectra of phosphorus oxychloride (OPCl₃) in the ground and excited vibrational states have been recorded and analyzed. The v₅ = 1 and v₆ = 1 state spectra show large splittings due to l resonance and the effect of the 2, -1 term r_t. Coriolis constants have been obtained for the two lowest degenerate states. The spectra of the asymmetric top species OP³⁵Cl₂³⁷Cl have been analyzed and centrifugal distortion constants obtained. These have been used to determine the harmonic force field of the molecule.     

Excited vibrational state microwave spectra,structure, and force-field of trifluorosilane

The J = 2?1 microwave spectrum of six isotopic species of HSiF₃ has been observed and assigned in excited states of five of the six fundamental vibrations. The assignment is based on relative intensities, double resonance experiments, and trial anharmonic force constant calculations. Analysis of the spectra leads to experimental values for five of the $\text{α}{}_{\mathrm{r}}{}^{\mathrm{B}}$ constants, all three l-doubling constants q_t, one Fermi resonance constant φ₂₃₃, and one zeta constant $\text{ζ}{}_{\mathrm{6,\; 6}}{}^{\mathrm{(z)}}$.The harmonic force field has been refined to all the available data on vibration wavenumbers, centrifugal distortion constants, and zeta constants. The cubic anharmonic force field has been refined to the data on $\text{α}{}_{\mathrm{r}}{}^{\mathrm{B}}$ and q_t constants, using two models: a valence force model with two cubic force constants for SiH and SiF stretching, and a more sophisticated model. With the help of these calculations, the following equilibrium structure has been determined: $\text{r}{}_{\mathrm{e}}\text{(}\text{SiH}\text{) = 1.4468(±5)}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(}\text{SiF}\text{) = 1.5624(±1)}\text{A}\text{?}$, ∠HSiF = 110.64(±3)°,