Microwave spectrum of 2-aminopyridine

The microwave spectra of 2-aminopyridine-NH₂, -ND₂, and of both of the two possible -NHD molecules have been observed and assigned in the 0⁺ vibrational state of the amino group inversion vibration; the assignment for three of the molecules in the 0⁻ state is also made. From intensity measurements the 0⁺-0⁻ splitting is estimated to be 135 ± 25 cm⁻¹ for the -NH₂ molecule and 95 ± 30 cm⁻¹ for the -ND₂ molecule. The rotational constants are interpreted in terms of a structure in which the amino group is bent about 32° out of the molecular plane, the c coordinates of the two amino H atoms being 0.21 and 0.28 Å. Stark effect measurements give a dipole moment of about 0.9 D which is almost entirely in the b axis, and which changes quite significantly between the 0⁺ and 0⁻ states.     

Microwave spectrum of 2-chloropyridine

The microwave spectrum of 2-chloropyridine, C₅H₄NCl, has been studied in the frequency range from 26.5–40.0 GHz. The spectrum is characterized by strong parallel type transitions of a near-prolate asymmetric top. The assigned transitions have been used to evaluate the ground state rotational constants of the two chlorine isotopes. The rotational constants are (in MHz): A = 5872.52, B = 1637.83, C = 1280.48 for the ³⁵Cl isotopic species and A = 5872.16, B = 1591.76, C = 1252.17 for the ³⁷Cl isotopic species. The small inertial defect indicates the molecule is planar. In addition an excited vibrational state of C₅H₄N³⁵Cl has been observed and analyzed. The chlorine quadrupolar coupling constants were determined for the ground state and are: χ_aa = ?71.9 MHz for ³⁵Cl and χ_aa = ?54.9 MHz for ³⁷Cl. By assuming the pyridine ring structure the CCl bond length is found to be 1.72 Å.     

Matrix-isolation study of the vacuum-ultraviolet photolysis of NF3: The electronic spectrum of the NF2 free radical

The vacuum-ultraviolet photolysis of NF₃ in an argon or a carbon monoxide matrix at 14°K leads to the production of NF₂, identified by its infrared absorption. F-atom photodetachment also leads to the appearance of FCO in the carbon monoxide matrix studies. The photodissociation of NF₂ by 2537 Å radiation has been confirmed. The appearance of a band system near 2600 Å with position and band spacings close to those previously reported for NF₂ in the gas phase demonstrates that the lower state of the gas-phase transition is the ground state of the molecule and confirms the assignment of the observed structure to a progression in the upper-state bending vibration.     

Microwave spectrum and hydrogen bonding in 2-dimethylaminoethanol

The microwave spectrum of the normal species of 2-dimethylaminoethanol gives rotational constants (MHz) A = 5814.0(2), B = 2214.54(2), and C = 2037.96(2) and a dipole moment of 2.56 D, with a, b, and c components (D) of 2.27(2), 0.3(1), and 1.16(5), respectively, consistent with a gauche OCCN configuration, and an OH?N type hydrogen bond, facilitated by a central CN configuration distorted approximately 23° from “staggered.” The hydroxy d₁ species rotational constants (MHz) A = 5688.95(38), B = 2190.17(4), and C = 2028.00(4) are consistent with either the hydroxyl group structure $\text{r}\text{OH = 1.235}\text{A}\text{?}$ and COH = 100.5° or a structurally normal hydroxyl group with an approximate 0.01 ÅrO?N shrinkage upon deuteration.     

Microwave spectrum and selenol internal rotation of 2-propaneselenol

Microwave spectra of 2-propaneselenol and its deuterated species were measured and assigned for the gauche and trans isomers. The double minimum splittings of the gauche isomers were directly observed from b-type transitions, which were assigned with the aid of a double resonance technique. Rotational constants and torsional splitting of the gauche isomer of the parent species were determined to be A = 7802.50 ± 0.75, B = 2847.68 ± 0.04, C = 2242.03 ± 0.03, ΔA = ?2.52 ± 0.74, ΔB = 0.02 ± 0.05, ΔC = ?0.34 ± 0.03, and Δν = 368.91 ± 0.94 MHz, where ΔA, and ΔB, and ΔC are the differences of the rotational constants between the (+) and (?) states. From the torsional splittings and the energy differences of the two isomers of the parent and SeD species, Fourier coefficients of the selenol internal rotation potential function were determined to be V₂ = ?88 ± 15, V₃ = 1543 ± 29 cal/mole on the assumption of V₁ = 0. Dipole moments and their components were also obtained for the two isomers.     

Microwave spectrum of ketene

A new Stark-modulated submillimeter-wave spectrometer is described. This spectrometer has been used to analyze the microwave spectrum of three isotopomers (heavy atoms) of ketene. The rotational constants determined have been used to calculate the structure of ketene using a variety of methods. The question of planarity of ketene is also addressed. High-resolution microwave measurements have been used to determine the spin-rotation interaction in CH₂¹³CO.     

Microwave spectrum of DNO

The microwave spectrum of deuterated nitroxyl DNO has been observed and analyzed. The molecule was produced by the reaction of D with NO in a flow system. Both a-type and b-type transitions have been observed and the resulting rotational constants, A = 315450.3 ± 4.8 MHz, B = 38731.5 ± 1.5 MHz, and C = 34354.0 ± 1.5 MHz, are in good agreement with those of the lower electronic state ¹A′ for the electronic transition of DNO observed by Dalby. The quadrupole coupling constants for nitrogen are χ_aa = 1.03 ± 0.40 MHz, χ_bb = −6.13 ± 0.26 MHz, χ_cc = 5.10 ± 0.26 MHz. The components of the electric dipole moment of DNO have been determined to be μ_a = 1.18 ± 0.04 D and μ_b = 1.22 ± 0.04 D, giving a total dipole moment μ_total = 1.70 ± 0.05 D. The half lifetime of the molecule varies from 1 to 40 sec, depending on the condition of the surfaces of the absorption cell, which is much longer than the values reported previously.     

Microwave spectrum of tropone

The microwave spectrum of tropone (2,4,6-cycloheptatriene-1-one) has been obtained and assigned. The observation of a statistical weight intensity alternation indicates that the molecule has C_2v symmetry. Relative intensity measurements show the molecule to possess a low wavenumber vibration whose 1-0 interval is 60 ± 20 cm^?1. The dipole moment is found to be 4.1 ± 0.3 D by the “rate-of-growth” method.     

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 spectrum of nitroxyl

The microwave spectrum of HNO has been observed and analyzed. Both a-type and b-type transitions have been measured. The rotational constants obtained are A = 553903.0 ± 2.7 MHz, B = 42308.52 ± 0.10 MHz, and C = 39169.46 ± 0.10 MHz. In the analysis of the spectrum, centrifugal distortion corrections are tentatively taken into account by using the centrifugal distortion constants determined by Dalby. The quadrupole coupling constants for nitrogen in HNO are determined to be χ_aa = 0.36 ± 0.56 MHz, χ_bb = ? 5.46 ± 0.30 MHz, and χ_cc = 5.10 ± 0.26 MHz. The dipole moment and its components determined from the Stark effect measurement are μ_total = 1.67 ± 0.03 D, μ_a = 1.03 ± 0.01 D, and μ_b = 1.31 ± 0.02 D. The microwave spectrum of DNO has been reanalyzed by taking into account the centrifugal distortion effect. The inertia defects for HNO and DNO have been calculated. The results are limited in precision by the lack of reliable force constants.     

Microwave spectrum of the HO2 radical

Rotational transitions of the HO₂ free radical, a type 1₀₁ ← 0₀₀, 2₀₂ ← 1₀₁, 2₁₂ ← 1₁₁, and 2₁₁ ← 1₁₀, and b type 6₁₆ ← 7₀₇, 7₁₇ ← 8₀₈, 9₀₉ ← 8₁₈, and 10_0,10 ← 9₁₉, have been observed up to 137 GHz with microwave spectroscopy. The rotational constants, the centrifugal distortion constants in the symmetric-top approximation, the spin-rotation coupling constants, and the coupling constants of Fermi contact and dipole-dipole interactions are determined accurately. The absolute value of ?_ab + ?_ba, the off-diagonal component of the spin-rotation interaction tensor, is obtained from its second-order perturbation contributions to the spin doublings of the b-type rotational transitions. The small value of the Fermi contact parameter leads to the conclusion that the hydroperoxyl radical is a π-electron radical. The lowest two K-type doubling transitions, which are of particular interest to radioastronomy, are predicted on the basis of the molecular constants obtained.     

Microwave spectrum of acetylene-d2

Eight P-branch transitions from the $\text{ν}{}_5{}^1\text{-ν}{}_4{}^1$ difference band of C₂D₂ have been observed in the microwave region. Significant improvements in the spectroscopic constants for the two states involved in the difference band have been obtained by combining infrared and microwave data. The Stark shifts for the observed C₂D₂ lines are discussed in some detail. The vibrational transition moment is found to be μ_vib = 0.0358 ± 0.0020 D.     

Microwave spectrum of fluoroacetyl chloride

The microwave spectrum of fluoroacetyl chloride has been studied in the 8–40 GHz region and transitions arising from one conformer have been assigned. This conformer has all the heavy atoms in a plane with the fluorine and chlorine atoms trans to one another. The rotational constants and nuclear quadrupole coupling constants for the ground vibrational state are (in MHz): H₂FCCO³⁵Cl: A = 9025.82, B = 2403.92, C = 1920.70, χ_aa = ?47.7, χ_bb = 23,7, χ_cc = 24.1; H₂FCCO³⁷Cl: A = 8994.95, B = 2342.24, C = 1879.75, χ_aa = ?38.0, χ_bb = 18.9, χ_cc = 19.1. The spectrum of the first excited torsional state has been assigned. Some lines possibly due to a second conformer have been observed but not yet assigned.     

Microwave spectrum of 3-iodopropene

The microwave spectra of 3-iodopropene were measured in the frequency region 12–18 GHz. The a-type R-branch and the b-type Q-branch rotational transitions of one conformer, skew, have been assigned and the rotational constants of the ground state have been obtained: A = 17 644.34, B = 1588.12, and C = 1538.64 MHz. The second-order quadrupole effects give rise to anomalous hyperfine splittings and are analyzed by taking into account χ_ab of the quadrupole coupling tensor. The nuclear quadrupole coupling constants have been determined to be χ_aa = ?1337, χ_bb = 387, χ_cc = 950, and ∥χ_ab∥ = 1081 MHz.     

Microwave spectrum of γ-valerolactone

An Ar⁺ laser at 4579 Å is used to excite the B¹Π_u-X¹Σ_g⁺ fluorescence of the ⁶Li⁷Li molecule in a crossed heat pipe oven. The spectrum in the region 4400–6300 Å is recorded photoelectrically with an emphasis on the observation of higher vibrational levels in the ground state close to the dissociation limit. P and R doublets corresponding to v″ ≤ 26 originating from the (v′ = 13, J′ = 19) level are observed and identified using mass-reduced quantum numbers. Two additional ⁶Li⁷Li series, known from earlier work of Velasco, Ottinger, and Zare, are also analyzed. These data are used to construct effective Rydberg-Klein-Rees (RKR) potentials for specific J″ (=9, 19) quantum numbers of the ground state and from them the true (rotationless) potential energy curve (for X¹Σ_g⁺) is derived. This extends the previously known curve of Li₂ from 4.28 to 5.18 Å (outer turning point); this turning point corresponds to an energy which is approximately 88% of the dissociation energy, which is estimated here to be 8516 ± 18 cm^?1.     

Microwave spectrum of 1,2-propanediol

The microwave spectrum of the sugar alcohol 1,2-propanediol (CH₃CHOHCH₂OH) has been measured over the frequency range 6.5–25.0 GHz with several pulsed-beam Fourier-transform microwave spectrometers. Seven conformers of 1,2-propanediol have been assigned and ab initio electronic structure calculations of the 10 lowest energy forms have been calculated. Stark effect measurements were carried out on several of the lowest energy conformers to provide accurate determinations of the dipole moment components and assist in conformer assignment.     

Microwave spectrum of 3-cyanocyclopropene

Microwave measurements of the normal isotopic species of 3-cyanocyclopropene have given the following ground vibrational state rotational constants: A = 19876.036 ± 0.006, B = 3533.743 ± 0.001, and C = 3417.839 ± 0.001 MHz. The value of the ¹⁴N quadrupole coupling constant χ_cc was found to be 1.62 ± 0.05 MHz, and the molecular dipole moment had a value of μ_T = 4.47 ± 0.04 Debye. The results are compared to those for related molecules, and are discussed qualitatively with respect to the molecular structure.