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1.
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 r(SBr) = 2.155 ± 0.006 A? and ? FSBr=100.6°±1.5° structural parameters when r(SO) = 1.407 A?, r(SF) = 1.56 A?, and ? OSO=123.7° are assumed.  相似文献   

2.
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 rs structural parameters of the gauche and trans isomers were determined. The structural parameters in the skeletal part for the gauche isomer are r(CC) = 1.524 A?, r(CSe) = 1.957 A?, r(SeH) = 1.467 A?, α(CCSe) = 113°31′, α(CSeH) = 93°05′, and the dihedral angle τ(CCSeH) = 61°39′. Those for the trans isomer are r(CC) = 1.525 A?, r(CSe) = 1.962 A?, r(SeH) = 1.440 A?, α(CCSe) = 108°43′, and α(CSeH) = 93°30′. These parameters were compared with the corresponding ones of ethanethiol.  相似文献   

3.
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Ca) = 1.0569 ± 0.001, r8(CaCb) = 1.2087 ± 0.001, r8(CbCc) = 1.3623 ± 0.003, r8(CcCd) = 1.2223 ± 0.004, r8(CdCe) = 1.3636 ± 0.003, r8(CeN) = 1.1606 ± 0.001 A? (10?10m). 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.  相似文献   

4.
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 rs and rm structures. The equilibrium structure, re, has been estimated by combining the rm parameters derived according to Watson's method and the re bond distances estimated in our recent electron-diffraction and spectroscopic studies to be re(CO) = 1.1756 ± 0.0023 A?, re(CCl) = 1.7381 ± 0.0019 A?, ∠eClCCl = 111.79 ± 0.24°.  相似文献   

5.
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 rz(CC) = 1.3391 ± 0.0013 A?, rz(CH) = 1.0869 ± 0.0013 A?, θz(CCH) = 121.28 ± 0.10°, and rz(CH) - rz(CD) = 0.00137 ± 0.00037 A?, where the errors include one standard deviation in the fitting and errors due to an uncertainty (±0.03°) in θz(CCH) - θz(CCD).  相似文献   

6.
The rz structure of phosgene has been determined by a joint analysis of the electron diffraction intensity and the rotational constants as follows: rz(CO) = 1.1785 ± 0.0026 A?, rz(CCl) = 1.7424 ± 0.0013 A?, ∠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 rz structure: a3(CO) = 2.9 ± 0.9 A??1, a3(CCl) = 1.6 ± 0.4 A??1. The equilibrium bond distances have been estimated from the rz structure for the normal species and from the anharmonic constants to be re(CO) = 1.1756 ± 0.0032 A?, re(CCl) = 1.7381 ± 0.0019 A?.  相似文献   

7.
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: rs(CS) = 1.554 ± 0.003 A?, rs(CC) = 1.314 ± 0.003 A?, rs(CH) = 1.090 ± 0.006 A?, ∠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.  相似文献   

8.
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: r (ClN) = 1.705 ± 0.005 A?; r (NC) = 1.226 ± 0.005 A?; r(CO) = 1.162 ± 0.005 A?; < (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.  相似文献   

9.
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 rRK 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 r(NH) = 0.995 A?, r(NC) = 1.314 A?, r(CO) = 1.668 A?, ∠HNC = 123.9°, and ∠NCO = 172.6°.  相似文献   

10.
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 C3v 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, DJ = 0.823 ± 0.092 kHz, DJK = 66.59 ± 0.18 kHz have been determined. From these data the following structural parameters have been derived: rs(CH) = 1.107 ± 0.001 A?, ∠s(HCC) = 110.30 ± 0.09°, rs(CC) = 1.465 ± 0.003 A?, r0(CP) = 1.544 ± 0.004 A?. 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 (vs = 1, 2, and 3) have been studied and various vibration-rotation parameters derived.  相似文献   

11.
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: re(CH) = 1.06215 ± 17 × 10?5A? and re(CC) = 1.20257 ± 9 × 10?5A? were obtained. This paper presents all the molecular constants derived in this study.  相似文献   

12.
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 rCC = 1.453(3) A?, rCC = 1.336(4) A?, 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.  相似文献   

13.
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 r(SiCl) = 2.055 ± 0.003 A?, r(SiC) = 1.845 ± 0.005 A?, ∠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 χaa = ?19.6 ± 0.3 MHz, χbb = ?3.7 ± 1.4 MHz, χcc = 23.3 ± 1.4 MHz, χbond = ?38.0 ± 1.6 MHz, and ηbond = 0.22 ± 0.08.  相似文献   

14.
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, K = 3 and 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 re structures for CHF3 and CDF3.The equilibrium structure was determined to be CH = 1.091 ± 0.014 A?, CF = 1.3284 ± 0.0031 A? and ∠FCF = 108.58 ± 0.34°.  相似文献   

15.
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: r0(BF) = 1.315 ± 0.006 A?, rs(BCl) = 1.728 ± 0.009 A?, < 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, ΔJK = 8.9 ± 1.7, and ΔJ = 1.86 ± 0.48 KHz. The asymmetry parameter κ = ?0.593291 and the inertial defect δ0 = 0.2361 amu Å2 which is consistent with that expected for this type of molecule if planar. The 35Cl quadrupole coupling constants for 11B35Cl19F2 are χaa = ?42.8 ± 1.0, χbb = 30.2 ± 1.5, χcc = 12.6 ± 1.5 MHz with the asymmetry parameter η = 0.41.  相似文献   

16.
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 DK = (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 r(CH) = 1.0854 ± 0.0005 A?, r(CCl) = 1.7760 ± 0.0003 A?, and <(HCH) = 110°.35 ± 0°.05.  相似文献   

17.
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: r(NH) = 0.993 A?, r(NC) = 1.207 A?, r(CS) = 1.5665 A?, ∠HNC = 131.7°, and ∠NCS = 173.8°. The molecule has the trans conformation.  相似文献   

18.
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 rCC(ring) = 1.453 ±0.025 A?, rCC(ald.) = 1.469 ± 0.010 A?, ∠CCC = 119.8 ± 2.0°. The dipole moments determined by means of the Stark effect are μa = 1.932 ± 0.005 D, μb = 1.511 ± 0.017 D, and μc = 0.277 ± 0.156 D, with μt = 2.469 ± 0.031 D.  相似文献   

19.
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 r(FC) = 1.285 ± 0.005 A? and r(CP) = 1.541 ± 0.005 A?. 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.  相似文献   

20.
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
rs(PCl)=2.0450±0.0072 A? ClPCl=100°12′±20′
rs(PCl)=2.0426±0.0005 A? ClPCl=100°6′±1′
  相似文献   

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