Microwave spectrum,structure, and nuclear quadrupole coupling of cis-1-chlorobutadiene-1,3

The microwave spectra of the two natural isotopic species of cis-1-chlorobutadiene-1,3, CH³⁵ClCHCHCH₂ and CH³⁷ClCHCHCH₂, together with all monosubstituted species with deuterium or ¹³C isotopes have been measured and assigned and the complete substitution structure has been determined. The spectral region investigated was between 18 and 40 GHz. The molecule was found to be planar and the following values were found for the principal parameters: r(CC)_chlorovinyl = 1.327(6), $\text{r(}\text{CC}\text{)}{}_{\mathrm{<mtext>vinyl</mtext>}}\text{= 1.343(2)}\text{A}\text{?}$, <(CCC)_chlorovinyl = 126.5(3)° and <(CCC)_vinyl = 123.0(7)°. The nuclear quadrupole coupling constants, χ_aa and χ_bb, for the parent molecule were calculated and further used to estimate the symmetry of the field gradient around the CCl bond. Force-field calculations were used to predict the centrifugal distortion constants and inertial defect of some isotopic species. Thermodynamic functions were calculated for cis- and trans-1-chlorobutadiene-1,3 and used to estimate the energy difference between them.     

New simple pulse sequences for distinguishing between CH3 and CH signals in 1H-noise-decoupled 13C NMR spectra

Combined pulse sequences are developed for partial suppressing of the ¹J(¹³C¹H) dependence of the APT measured intensities of ¹³C signals. The sequences contain one or several time periods with different lengths τ without irradiation by the decoupler field. Consequently the relative intensities of CH₃ and CH signals have unequivocally separated fields of values for the range of expected coupling constants.     

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.     

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.     

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).     

Vibration-torsion interaction in the microwave spectrum of internally hydrogen-bonded methylmalonaldehyde

The microwave spectrum of methylmalonaldehyde has been measured and the molecule shown to be in an intramolecularly hydrogen-bonded (chelate ring) form in the gas phase. The spectrum shows the effects of two large amplitude internal motions: the torsion of the methyl group about its symmetry axis and the tunneling of the hydrogen-bond hydrogen through a potential barrier to an equivalent position (combined with an appropriate CH₃ rotation). The two motions are coupled through the torsion-inversion potential energy term of threefold symmetry in the torsional coordinate. A two vibration-plus-rotation model is developed and applied to explain the sizeable perturbations of the pure rotational transitions from a rigid rotor pattern in four ground-state sublevels. The observed torsion-inversion splittings in the nondegenerate level (2.8004 cm^?1 for $\text{OCHC(CH}{}_3\text{)CHOH}$, 0.35920 cm^?1 for $\text{OCHC(CH}{}_3\text{)CHOD}$ and 0.92590 cm^?1 for $\text{OCHC(CD}{}_3\text{)CHOH)}$ are quite well determined and, as expected, depend strongly upon appropriate isotopic substitutions. The experimentally derived parameters are discussed in terms of an effective inversion-torsion potential surface. The data are not in disagreement with a range of barrier values determined from comparison of ab initio full geometry-optimized and constrained C_2v geometry-optimized molecular orbital calculations. Because of the expected isotope dependence of the effective surface and the large number of parameters involved, it is not clear whether more accurate fitting to the data is justified.     

Pressure-induced H2 opacity in the 5-μm region

The H₂ opacity arising from the pure-rotational hexadecapole-induced U₀(J) transitions occurring during H₂H₂ and H₂He collisions, and from the hexadecapole-induced U₀(J) + S₀(J′) and the quadrupole-induced S₀(J) + S₀(J′) transitions in H₂He collisions, has been calculated. The U₀(J) and S₀(J) + S₀(J′) contributions from H₂H₂ collisions are important H₂ opacities in the frequency range from 700–3000 cm^?1 for temperatures appropriate to the outer planets. It is concluded that this opacity is needed in addition to the opacity from the extrapolation of the 0-0 and 1-0 H₂H₂ collisionally induced bands to interpret the spectrum at 5 μm for the outer planets.     

The microwave spectrum of 1-phenylphosphaethyne,C6H5CP

The molecule 1-phenylphosphaethyne, C₆H₅CP, was detected by microwave spectroscopy when Ph(Me₃Si)CPCl was pyrolyzed in the gas phase at 750°C. Asymmetric rotor transitions between 26.5 and 40 GHz with J = 16 to 22 were analyzed to yield A₀ = 5669.044(72), B₀ = 933.79209(71), and C₀ = 801.59279(75). These data indicate that the bond length r(CC) between the ring and CP group carbon atom is 1.467 Å.     

An out-of-plane force field for p-benzoquinone and some structurally related molecules

A simplified out-of-plane valence force field in the harmonic approximation has been constructed for ethene, butadiene, glyoxal, acrolein, and p-benzoquinone using the overlay technique. p-Benzoquinone is considered to consist of two conjugated OCCHCHCO systems and force constants from the first four mentioned molecules are shown to be successfully transferable to p-benzoquinone. The force field has 21 independent parameters and gives a root-mean-square frequency error of 7.61 cm^?1.     

A comparative ab initio study of the structures,dipole moments,force fields,and anharmonic frequencies of formamide and thioformamide

The structures, dipole moments, force fields, and anharmonic frequencies for the planar conformation of formamide and thioformamide were calculated using the unscaled 4-31G basis set, augmented with a full set of d functions on the sulfur, and full geometry optimization. Extensive comparison of the geometries are made, especially the CO and CS bond lengths, with both the experimental values for the amides and values calculated in previous studies on the acids and other carbonyl compounds. Comparison of the dipole moments calculated using the optimized and experimental geometries with the experimental values suggest there is some inconsistancy in the experimental geometry for thioformamide. Quadratic, cubic, and quartic force constants are calculated for both amides, and hence the fundamental vibration frequencies. Critical comparisons are made with the assignments based on experimental observations. Differences in the bond lengths and stretching force constants for the two NH bonds are shown to be consistent with a hydrogen-bonding type of interaction between the proximal NH and CO and CS groups, like that in the acids.     

Tunable laser Stark-difference spectra of CD3OH

We present Doppler resolution limited spectra of the P(J) and R(J) multiplets for J ≦ 10 of the 10-μm CO stretch band of ¹²CD₃¹⁶OH using a tunable diode laser. Relative frequencies within the multiplets accurate to ±0.0002–0.0005 cm^?1 are obtained, but no absolute frequencies are given. We are able to assign most of the hindered rotation and K substructure in these multiplets. The assignments are based on analyses of Stark-difference spectra combined with the ground-state microwave data and the intensity variations which are expected theoretically. The ground and excited state A, K = 1 asymmetry splitting parameters are measured to be δ₁″ = (8.5450 ± 0.0080) × 10^?3cm^?1 and δ₁′ = (9.7706 ± 0.0080) × 10^?3cm^?1, respectively. The ground-state value agrees well with the microwave results. A rapid-scan system for recording data and a computer-aided technique for calibrating and plotting the spectra are described.     

The microwave spectrum of methylene ketene

The microwave spectrum of methylene ketene has been observed from 8 to 35 GHz and assigned. Rotational constants and centrifugal distortion constants have been determined for CH₂CCO, CHDCCO, and CD₂CCO. The dipole moment was found to be μ_a = 2.14 ± 0.06 D (7.07 ± 0.2 × 10^?30 Cm). We were unable to detect propynal among the pyrolysis products of acrylic anhydride. This pyrolysis proved to be the most convenient route for generating methylene ketene for the present investigation.     

Investigation of the ν5 band of methylacetylene by infrared laser Stark and microwave spectroscopy

Microwave spectra have been studied in the ground and v₅ = 1 (CC stretching mode) states of methylacetylene. From these data, dipole moments and rotational and centrifugal distortion constants have been determined, as follows: μ_D⁽⁰⁾ = 0.7839 ± 0.0010 D, μ_D⁽⁵⁾ = 0.7954 ± 0.0010 D, B₅ = 8508.119 ± 0.003 MHz, D_J⁽⁵⁾ = 1.8 ± 0.2 kHz, and D_JK⁽⁵⁾ = 169 ± 1 kHz. Laser Stark spectra have been obtained for the ν₅ band of this molecule and from these spectra the following vibration-rotation parameters have been determined: ν₅⁰ = 93.27540 ± 0.00007 cm^?1, A₅ - A₀ = ?227.0 ± 2.3 MHz and D_K⁽⁵⁾ - D_K⁽⁰⁾ = ?0.05 ± 0.50 MHz. The higher-J and -K states of the v₅ = 1 state appear to be purturbed.     

Microwave and infrared spectra of isotopically substituted carbonyl selenide (OCSe)

Infrared and microwave spectral measurements are given for three isotopically enriched species of carbonyl selenide. The high-resolution infrared measurements (made near 2000 and 2600 cm^?1) provide constants for the following transitions: 10⁰000⁰0 for ¹⁶O¹²C⁸⁰Se; 10⁰000⁰0 and 11¹001¹0 for ¹⁸O¹²C⁸⁰Se; and 10⁰000⁰0, 11¹001¹0, 10⁰100⁰1, and 10⁰100⁰0 for ¹⁶O¹³C⁸⁰Se. Microwave measurements are given for the J = 4 ← 3, and 3 ← 2 transitions of ¹⁸O¹²C⁸⁰Se and ¹⁶O¹³C⁸⁰Se in the 00⁰0, 01¹0, 02⁰0, 02²0, and 00⁰1 states. Equilibrium rotational constants are given for all three isotopic species and the equilibrium bond distances are determined to be $\text{r}{}_{\mathrm{e}}\text{(CO) = 1.1535 ± 0.0001}\text{A}\text{?}$ and $\text{r}{}_{\mathrm{e}}\text{(CSe) = 1.7098 ± 0.0001}\text{A}\text{?}$.     

Infrared diode laser spectroscopy of FCO: The ν1 and ν2 bands

The ν₁ (CO stretching) and ν₂ (CF stretching) bands of the FCO radical were observed with Doppler-limited resolution by an infrared diode laser spectrometer with Zeeman and source modulation. The FCO radical was generated by a 60-Hz discharge in one of the following three gas mixtures: O₂ + C₂F₄, CO + SF₆, and CO + C₂F₄, all diluted with He. The observed spectra were analyzed to determine the rotational constants, the centrifugal distortion constants, and the spin-rotation interaction constants. The band origins, 1861.6372(1) and 1026.1283(1) cm^?1 [with standard errors in parentheses], which were obtained, were found to agree well with matrix data, 1857 and 1023 cm^?1, respectively. The assignment of the observed spectra to the FCO radical was further supported by observing the ν₁ band of F¹³CO, which was obtained from ¹³CO and SF₆. The molecular structure and the force field of FCO are briefly discussed by using molecular constants obtained from the observed spectra.     

Level-Crossing-Untersuching der Stark-Aufspaltung der tiefsten1 P 1-Terme von Ca,Sr und Ba

Using the level-crossing technique, magnitude and sign of the tensor polarizability α_ten of the lowest¹ P ₁-levels of Ca, Sr, and Ba have been measured by investigating the splitting into Zeeman-sublevels in superimposed homogeneous electric and magnetic fields. The experimental results are: α_ten/g _J =?13.6(3) kHz/(kV/cm)² for Ca α_ten/g _J =?14.32(15) kHz/(kV/cm)² for Sr α_ten/g _J =?10.72(10) kHz/(kV/cm)² for Ba, where theg _J -values are approximatelyg _J≈1. With greater accuracy the ratios of these constants have been determined by eliminating the electric-field strength measurement: (α_ten(Sr)/g _J (Sr))/(α_ten(Ca)/g _J (Ca))=1.050(8) (α_ten(Sr)/g _J (Sr))/(α_ten(Ba)/g _J (Ba))=1.336(2). The polarizability constants are discussed with regard to the state vectors of the lowestsp ¹ P ₁- and³ P ₁-levels. The tensor polarizability of the 6s 6p¹ P ₁-level of Ba I is considered in relation to oscillator strengths of electric dipole transitions to neighbouring levels.     

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 $\text{r}{}_{\mathrm{e}}\text{(}\text{CO}\text{) = 1.1756 ± 0.0032}\text{A}\text{?}$, $\text{r}{}_{\mathrm{e}}\text{(}\text{CCl}\text{) = 1.7381 ± 0.0019}\text{A}\text{?}$.     

cis Acrolein: Mixing of the S0 and S1 electronic states by the (a″) skeletal torsional vibration

Large effects of vibronic coupling upon vibrational levels of the ground (¹A′) and first excited (¹A″) singlet electronic states of cis acrolein (2-propenal) are successfully modeled. Some implications for CH₂CHCHO spectroscopy and photophysics are discussed briefly.     

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.     

Infrared-microwave double resonance in CH3OH using a Zeeman-tuned 3.5-μm HeXe laser

Infrared microwave double resonance signals have been observed for CH₃OH using the 3.5-μm HeXe laser line. When microwave transitions in the ground vibrational state are pumped, the double resonance signals are obtained on two infrared transitions v = 1 ← 0 of ν^CH(a′); v = 1, J, K, μ = 4, 2, 1 ← v = 0, J, K, μ = 3, 2, 1, and 4, 3, 1 ← 3, 3, 1. Three weak double resonance signals are due to the collision-induced transitions. Their relative intensities have been explained successfully by using the rate constants of collision-induced transitions which are proportional to the dipole matrix elements between the states involved in the transitions.