Rotational spectrum of sulfuryl bromide fluoride

The rotational spectra of SO₂⁷⁹BrF and SO₂⁸¹BrF have been obtained between 18 and 40 GHz. Both molecules are near-prolate symmetric rotors with a and b-type dipole components. A least-squares fit of the observed moments of inertia obtained by correcting for the bromine quadrupole interaction yields $\text{r}\text{(SBr) = 2.155 ± 0.006}\text{A}\text{?}$ and ? FSBr=100.6°±1.5° structural parameters when $\text{r}\text{(SO) = 1.407}\text{A}\text{?}$, $\text{r}\text{(SF) = 1.56}\text{A}\text{?}$, and ? OSO=123.7° are assumed.     

The microwave spectrum,substitution structure and dipole moment of cyanobutadiyne,HCCCCCN

Cyanobutadiyne (cyanodiacetylene), HCCCCCN, is sufficiently stable at low pressures to permit its rotational spectrum to be studied by microwave spectroscopy. The spectrum consists of a series of R-branch transitions typical of a linear molecule. The transitions with J = 9 to 14 which lie between 26.5 and 40.0 GHz have been measured for the vibrational ground state. Transitions have also been detected in natural abundance for all possible singly substituted ¹³C and ¹⁵N isotopic species. Deuteriated cyanobutadiyne, DCCCCCN, has also been synthesized and its ground state spectrum recorded. These measurements have enabled a complete substitution structure to be derived for the first time for a polyacetylene: r₈(HC_a) = 1.0569 ± 0.001, r₈(C_aC_b) = 1.2087 ± 0.001, r₈(C_bC_c) = 1.3623 ± 0.003, r₈(C_cC_d) = 1.2223 ± 0.004, r₈(C_dC_e) = 1.3636 ± 0.003, $\text{r}{}_8\text{(}\text{C}{}_{\mathrm{e}}\text{}\text{N}\text{) = 1.1606 ± 0.001}\text{A}\text{?}\text{(10}{}^{\mathrm{?10}}\text{m}\text{)}$. The spectroscopic parameters for the ground state are B₀ = 1331.3313 ± 0.001 MHz and D₀ = 0.0257 ± 0.002 KHz. The dipole moment, determined from the Stark effects of the J = 9 and 10 lines, is 4.33 ± 0.03 Debye.     

Internal rotation and molecular structure of ethaneselenol by microwave spectroscopy

The microwave spectra of ethaneselenol and its deuterated and ¹³C-substituted species were measured and assigned for the gauche and trans isomers. The double minimum splittings in the gauche isomers were directly observed for the species having a symmetry plane in the frame part. The rotational constants and the torsional splitting of the gauche isomer of the parent species were determined to be A = 27 148.86 ± 0.05, B = 3 623.68 ± 0.01, C = 3 399.21 ± 0.03, and Δν = 1 083.33 ± 0.04 MHz. From the torsional splittings of the parent and SeD species together with the vibrational frequencies already reported by Durig and Bucy, the Fourier coefficients of the selenol internal rotation potential function were determined to be V₁ = ?44 ± 17, V₂ = ?260 ± 3, V₃ = 1202 ± 16, and V₆ = ?43 ± 9 cal/mole. From the rotational constants obtained, the r_s structural parameters of the gauche and trans isomers were determined. The structural parameters in the skeletal part for the gauche isomer are $\text{r}\text{(CC) = 1.524}\text{A}\text{?}$, $\text{r}\text{(CSe) = 1.957}\text{A}\text{?}$, $\text{r}\text{(SeH) = 1.467}\text{A}\text{?}$, α(CCSe) = 113°31′, α(CSeH) = 93°05′, and the dihedral angle τ(CCSeH) = 61°39′. Those for the trans isomer are $\text{r}\text{(CC) = 1.525}\text{A}\text{?}$, $\text{r}\text{(CSe) = 1.962}\text{A}\text{?}$, $\text{r}\text{(SeH) = 1.440}\text{A}\text{?}$, α(CCSe) = 108°43′, and α(CSeH) = 93°30′. These parameters were compared with the corresponding ones of ethanethiol.     

Molecular structure of phosgene as studied by gas electron diffraction and microwave spectroscopy: The rs,rm, and re structures

The microwave spectra of eight isotopic species of COCl₂ have been observed, and the following rotational constants have been obtained: An analysis of the rotational constants has resulted in the r_s and r_m structures. The equilibrium structure, r_e, has been estimated by combining the r_m parameters derived according to Watson's method and the r_e bond distances estimated in our recent electron-diffraction and spectroscopic studies to be $\text{r}{}_{\mathrm{e}}\text{(CO}\text{) = 1.1756 ± 0.0023}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(CCl}\text{) = 1.7381 ± 0.0019}\text{A}\text{?}$, ∠_eClCCl = 111.79 ± 0.24°.     

Microwave spectra of deuterated ethylenes: Dipole moment and rz structure

The pure rotational spectra of three deuterated ethylenes, CH₂CD₂, CH₂CHD, and cis-CHDCHD, were observed by microwave spectroscopy, and the rotational and centrifugal distortion constants were determined precisely. The dipole moment of CH₂CD₂ was calculated from the Stark effects to be 0.0091 ± 0.0004 D. From the observed rotational constants the average structure was calculated to be $\text{r}{}_{\mathrm{z}}\text{(CC)}\text{= 1.3391 ± 0.0013}\text{A}\text{?}$, $\text{r}{}_{\mathrm{z}}\text{(CH)}\text{= 1.0869 ± 0.0013}\text{A}\text{?}$, θ_z(CCH) = 121.28 ± 0.10°, and $\text{r}{}_{\mathrm{z}}\text{(CH)}\text{- r}{}_{\mathrm{z}}\text{(CD)}\text{= 0.00137 ± 0.00037}\text{A}\text{?}$, where the errors include one standard deviation in the fitting and errors due to an uncertainty (±0.03°) in θ_z(CCH) - θ_z(CCD).     

Molecular structure of phosgene as studied by gas electron diffraction and microwave spectroscopy: The rz structure and isotope effect

The r_z structure of phosgene has been determined by a joint analysis of the electron diffraction intensity and the rotational constants as follows: $\text{r}{}_{\mathrm{z}}\text{(}\text{CO}\text{) = 1.1785 ± 0.0026}\text{A}\text{?}$, $\text{r}{}_{\mathrm{z}}\text{(}\text{CCl}\text{) = 1.7424 ± 0.0013}\text{A}\text{?}$, ∠_z;ClCCl = 111.83 ± 0.11°, where uncertainties represent estimated limits of experimental error. The effective constants representing bond-stretching anharmonicity have been obtained from an analysis of the isotopic differences in the r_z structure: $\text{a}{}_3\text{(}\text{CO}\text{) = 2.9 ± 0.9}\text{A}\text{?}{}^{\mathrm{?1}}$, $\text{a}{}_3\text{(}\text{CCl}\text{) = 1.6 ± 0.4}\text{A}\text{?}{}^{\mathrm{?1}}$. The equilibrium bond distances have been estimated from the r_z structure for the normal species and from the anharmonic constants to be $\text{r}{}_{\mathrm{e}}\text{(}\text{CO}\text{) = 1.1756 ± 0.0032}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(}\text{CCl}\text{) = 1.7381 ± 0.0019}\text{A}\text{?}$.     

The microwave spectrum,substitution structure,and dipole moment of thioketen,H2CCS

The microwave spectrum of the unstable thiocarbonyl thioketen, H₂CCS, has been investigated in the region 26.5–40 GHz. All singly substituted species as well as D₂CCS have been studied and the derived rotational constants yield the following structural parameters: $\text{r}{}_{\mathrm{<mtext>s</mtext>}}\text{(CS) = 1.554 ± 0.003}\text{A}\text{?}$, $\text{r}{}_{\mathrm{<mtext>s</mtext>}}\text{(CC) = 1.314 ± 0.003}\text{A}\text{?}$, $\text{r}{}_{\mathrm{<mtext>s</mtext>}}\text{(CH) = 1.090 ± 0.006}\text{A}\text{?}$, ∠_s(HCH) = 120.3 ± 0.5°. The dipole moment is μ = 1.02 ± 0.01 D. Four low frequency vibrational modes have been observed and their assignments are discussed.     

Further study of the microwave spectrum of chlorine lsocyanate: The substitution structure and nuclear quadrupole coupling

The microwave spectra of three further isotopic species of chlorine isocyanate (³⁵Cl¹⁵N¹²C¹⁶O, ³⁷Cl¹⁵N¹²C¹⁶O, ³⁵Cl¹⁴N¹³C¹⁶O) have been measured. From them we have obtained rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants. The data are combined with earlier data (1) to confirm the planarity of the molecule, and to give a full substitution structure as follows: $\text{r}\text{(ClN) = 1.705 ± 0.005}\text{A}\text{?}$; $\text{r}\text{(NC) = 1.226 ± 0.005}\text{A}\text{?}$; $\text{r}\text{(CO) = 1.162 ± 0.005}\text{A}\text{?}$; < (ClNC) = 118°50′ ± 30′; < (NCO) = 170°52′ ± 30′, with Cl and O trans. We have also calculated the chlorine and nitrogen quadrupole coupling constants using the SCF-MO-CNDO method, and have obtained good agreement with the measured values. Evidence for in-plane π-bonding at nitrogen has been obtained.     

Molecular structure and centrifugal distortion constants of isocyanic acid from the microwave,millimeter wave,and far-infrared spectra

The pure rotational spectra of HNCO and DNCO were measured in the far-infrared region from 80 to 350 cm^?1 by a Fourier transform spectrometer with a resolution of 0.1 cm^?1. The ^rR_K branches were measured and assigned for HNCO from K = 1 to 6, and for DNCO from K = 3 to 8. The measured transition wavenumbers were analyzed together with the microwave and millimeter wave data reported by Hocking, Gerry, and Winnewisser [Can. J. Phys.53, 1869–1901 (1975)] and with the far-infrared data of Krakow, Lord, and Neely [J. Mol. Spectrosc.27, 148–176 (1968)] in the low-wavenumber region. The microwave and millimeter wave data of H¹⁵NCO, HN¹³CO, and HNC¹⁸O reported by Hocking et al. were reanalyzed assuming several centrifugal distortion constants to be identical with those of the normal species. The molecular structure of HNCO was reevaluated using a modified substitution method from the rotational constants obtained in this work. The molecule has a bent structure in a trans configuration with $\text{r}\text{(NH) = 0.995}\text{A}\text{?}$, $\text{r}\text{(NC) = 1.314}\text{A}\text{?}$, $\text{r}\text{(CO) = 1.668}\text{A}\text{?}$, ∠HNC = 123.9°, and ∠NCO = 172.6°.     

The microwave spectrum of 1-phosphapropyne,CH3CP: Molecular structure,dipole moment,and vibration-rotation analysis

The J = 4 ← 3 and J = 3 ← 2 rotational transitions of 1-phosphapropyne, CH₃CP, between 26.5 and 40 GHz have been studied by microwave spectroscopy. The spectrum shows the characteristic vibration-rotation satellite patterns associated with a C_3v symmetric rotor. Apart from the most abundant isotope variant, the species ¹²CD₃¹²C³¹P, ¹²CD₂H¹²C³¹P, ¹²CH₂D¹²C³¹P, ¹³CH₃¹²C³¹P, ¹²CH₃¹³C³¹P, ¹³CD₃¹²C³¹P, and ¹²CD₃¹³C³¹P have also been studied. For ¹²CH₃¹²C³¹P the rotational constants B₀ = 4991.339 ± 0.003 MHz, D_J = 0.823 ± 0.092 kHz, D_JK = 66.59 ± 0.18 kHz have been determined. From these data the following structural parameters have been derived: $\text{r}{}_{\mathrm{s}}\text{(}\text{CH}\text{) = 1.107 ± 0.001}\text{A}\text{?}$, ∠_s(HCC) = 110.30 ± 0.09°, $\text{r}{}_{\mathrm{s}}\text{(}\text{CC}\text{) = 1.465 ± 0.003}\text{A}\text{?}$, $\text{r}{}_0\text{(}\text{CP}\text{) = 1.544 ± 0.004}\text{A}\text{?}$. The dipole moment has been determined as 1.499 ± 0.001 D by analysis of the Stark effect of the J = 3 ← 2, |K| = 1 line. The vibrational satellites (v_s = 1, 2, and 3) have been studied and various vibration-rotation parameters derived.     

Infrared bands of 12C2HD

The rotational structure of about 40 bands of ¹²C₂HD observed in the region 6000?600 cm^?1 has been measured and interpreted with the purpose of determining a comprehensive set of molecular constants for this isotopic variety of acetylene. Combining these data with the results for ¹²C₂H₂ and ¹²C₂D₂, a reevaluation of the equilibrium internuclear distances for the acetylene molecule has been made: $\text{r}{}_{\mathrm{e}}\text{(CH) = 1.06215 ± 17 × 10}{}^{\mathrm{?5}}\text{A}\text{?}$ and $\text{r}{}_{\mathrm{e}}\text{(CC) = 1.20257 ± 9 × 10}{}^{\mathrm{?5}}\text{A}\text{?}$ were obtained. This paper presents all the molecular constants derived in this study.     

Microwave spectrum of 2-propene-1-imine,CH2CHCHNH

The reactive species, 2-propene-1-imine, has been identified by its microwave spectrum as a pyrolysis product of diallylamine vapor (100 mTorr, 400°C). Two entirely planar forms are observed, both with an “s-trans” CCCN configuration. The lower energy rotamer has an “anti” CCNH configuration, with $\text{r}\text{CC = 1.453(3)}\text{A}\text{?}$, $\text{r}\text{CC = 1.336(4)}\text{A}\text{?}$, and ∠ CCC = 122.9(3)° and a dipole moment of 2.01(2) D with 1.13(1) D and 1.66(2) D “a” and “b” components. The higher energy rotamer has a “syn” CCNH configuration and a dipole moment of 2.51(2) D with 2.39(2) and 0.77(3) D the “a” and “b” components. From relative intensity measurements, the ground state energy difference is determined to be 0.9 ± 0.1 kcal mole^?1.     

Microwave spectrum of dimethyldichlorosilane

The microwave spectrum of dimethyldichlorosilane has been observed and the rotational constants and centrifugal distortion constants have been determined for ³⁵Cl₂ and ³⁵Cl³⁷Cl species. From these constants, the molecular structure is determined as $\text{r(}\text{SiCl}\text{) = 2.055 ± 0.003}\text{A}\text{?}$, $\text{r(}\text{SiC}\text{) = 1.845 ± 0.005}\text{A}\text{?}$, ∠ClSiCl = 107.2 ± 0.3°, ∠CSiC = 114.7 ± 0.3°. An analysis of the ³⁵Cl₂ quadrupole splittings leads to quadrupole coupling constants of χ_aa = ?19.6 ± 0.3 MHz, χ_bb = ?3.7 ± 1.4 MHz, χ_cc = 23.3 ± 1.4 MHz, χ_bond = ?38.0 ± 1.6 MHz, and η_bond = 0.22 ± 0.08.     

Microwave l-type resonance transitions of the v6 = 1 state in CHF3 and CDF3: Accidental degeneracy and molecular structure

Observations of the direct l-type resonance transitions in the microwave spectrum of the v₆ = 1 state of CHF₃ and CDF₃ have been extended to J = 37. Accidental degeneracies were found between J = 34, $\text{K}\text{= 3}\text{and}\text{0}$ in both molecules enabling the C rotational constants of CHF₃ and CDF₃ to be determined, using 118 observed frequencies for CHF₃ and 104 for CDF₃. After suitable correction the B and C rotational constants were used to determine the r₀, r₂, and r_e structures for CHF₃ and CDF₃.The equilibrium structure was determined to be $\text{CH}\text{= 1.091 ± 0.014}\text{A}\text{?}$, $\text{CF}\text{= 1.3284 ± 0.0031}\text{A}\text{?}$ and ∠FCF = 108.58 ± 0.34°.     

The microwave spectrum,structure, and quadrupole coupling constants of boron chloride difluoride,BCIF2

The microwave spectrum of boron chloride difluoride, BClF₂, has been investigated in the region 26.5–40.0 GHz. R-branch transitions belonging to the isotopic species ¹¹B³⁵Cl¹⁹F₂, ¹¹B³⁷Cl¹⁹F₂, and ¹⁰B³⁵Cl¹⁹F₂ have been observed and the derived rotational constants yield the following ground-state structural parameters: $\text{r}{}^0\text{(BF) = 1.315 ± 0.006}\text{A}\text{?}$, $\text{r}{}^{\mathrm{s}}\text{(BCl) = 1.728 ± 0.009}\text{A}\text{?}$, < FBF = 118.1 ± 0.5°. The ground-state rotational constants of the most abundant species ¹¹B³⁵Cl¹⁹F₂ are: A₀ = 10 449.32 ± 0.13, B₀ = 4705.811 ± 0.020, C₀ = 3239.702 ± 0.026 MHz, Δ_JK = 8.9 ± 1.7, and Δ_J = 1.86 ± 0.48 KHz. The asymmetry parameter κ = ?0.593291 and the inertial defect δ⁰ = 0.2361 amu Ų which is consistent with that expected for this type of molecule if planar. The ³⁵Cl quadrupole coupling constants for ¹¹B³⁵Cl¹⁹F₂ are χ_aa = ?42.8 ± 1.0, χ_bb = 30.2 ± 1.5, χ_cc = 12.6 ± 1.5 MHz with the asymmetry parameter η = 0.41.     

Determination of A0 for CH335Cl and CH337Cl from the ν4 infrared and Raman bands

The ν₄ infrared and Raman bands of CH₃Cl were analyzed simultaneously. A direct fit yielded a complete set of constants for CH₃³⁵Cl, including A₀ = 5.20530 ± 0.00010 cm^?1 and D_K = (8.85 ± 0.13) × 10^?5cm^?1. For CH₃³⁷Cl an incomplete set of constants was obtained from the infrared band, and A₀ = 5.2182 ± 0.0010 cm^?1 was estimated by curve fitting of the Raman spectrum. The resulting equilibrium structure is $\text{r(}\text{CH) = 1.0854 ± 0.0005}\text{A}\text{?}$, $\text{r(}\text{CCl) = 1.7760 ± 0.0003}\text{A}\text{?}$, and <(HCH) = 110°.35 ± 0°.05.     

Ground state spectroscopic constants of H15NCS,HN13CS,and HNC34S,and the molecular structure of isothiocyanic acid

The rotational spectrum of isothiocyanic acid was measured for the isotopically enriched species H¹⁵NCS and HN¹³CS as well as HNC³⁴S in natural abundance. In the frequency range from 8 to 240 GHz the a-type R-branch transitions were measured for all three isotopic species. The ^qQ₁ transitions were identified in the microwave region for H¹⁵NCS and HN¹³CS. The rotational and centrifugal distortion constants were determined using Watson's Hamiltonian in the S reduction, extended empirically to higher order terms in the angular momentum. The molecular structure of isothiocyanic acid was reevaluated using a modified substitution method and the NCS chain was found to be bent: $\text{r(}\text{NH}\text{) = 0.993}\text{A}\text{?}$, $\text{r(}\text{NC}\text{) = 1.207}\text{A}\text{?}$, $\text{r(}\text{CS}\text{) = 1.5665}\text{A}\text{?}$, ∠HNC = 131.7°, and ∠NCS = 173.8°. The molecule has the trans conformation.     

Microwave spectrum,torsional excitation energy,partial structure,and dipole moment of oxiranecarboxaldehyde

The microwave spectrum of oxiranecarboxaldehyde (glycidaldehyde) has been studied in the 8–40 GHz region. Transitions in the ground and first seven excited states of the torsional motion of the aldehyde group have been assigned for the species with the oxygen atom of the aldehyde group trans to the oxirane ring. The v = 0 to v = 1 torsional excitation energy is estimated to be 140 ± 10 cm^?1. The population of any other torsional conformer is less than 5% of the trans species at 200 K. Structural parameters were derived from rotational constants of the three singly substituted ¹³C species, whose spectra were observed in natural abundance. Substitution parameters are $\text{r}{}_{\mathrm{<mtext>CC</mtext>}}\text{(ring) = 1.453 ±0.025}\text{A}\text{?}$, $\text{r}{}_{\mathrm{<mtext>CC</mtext>}}\text{(ald.) = 1.469 ± 0.010}\text{A}\text{?}$, ∠CCC = 119.8 ± 2.0°. The dipole moments determined by means of the Stark effect are μ_a = 1.932 ± 0.005 D, μ_b = 1.511 ± 0.017 D, and μ_c = 0.277 ± 0.156 D, with μ_t = 2.469 ± 0.031 D.     

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.     

Force constant calculations of NCl3 and PCl3

A method based on the least-squares fitting of the observed vibrational frequencies, centrifugal distortion constants, mean-square amplitudes, and vibration-rotation interaction constants with respect to the harmonic force constants has been employed to determine the harmonic force field of NCl₃ and PCl₃. The results are compared with those obtained by other authors. An improved structure of PCl₃ has also been determined by analysis of the microwave spectrum of the P³⁷Cl₃ and P³⁵Cl₂³⁷Cl isotopic species. Two structures have been obtained with the following values of the parameters

$\text{r}{}_{\mathrm{s}}\text{(PCl)=2.0450±0.0072}\text{A}\text{?}\text{Cl}\text{P}\text{Cl=100°12′±20′}$

$\text{r}{}_{\mathrm{s}}\text{(PCl)=2.0426±0.0005}\text{A}\text{?}\text{Cl}\text{P}\text{Cl=100°6′±1′}$