Fourier transform microwave spectrum of the CO-dimethyl sulfide complex

The rotational spectrum of the CO-dimethyl sulfide (DMS) complex was measured in the frequency region from 4.8 up to 25 GHz by Fourier transform microwave spectroscopy. For the normal species 27 a-type and 57 c-type transitions were observed, while 16 and 8 c-type transitions were assigned for the species with ³⁴S and ¹³C in the DMS moiety, respectively, in natural abundance. In addition, 7 a-type and 48 c-type transitions were assigned for the complex with the ¹³CO enriched species as a component and 9 a-type and 42 c-type transitions for the complex with enriched C¹⁸O. No splitting was observed, which could be ascribed to the tunneling motion of the CO between two possible potential minima around DMS, while many transitions were split by the internal-rotation of the two methyl tops of the DMS unit. In cases where the K-type splitting was close to the methyl internal-rotation splitting, forbidden transitions were observed which apparently followed b-type selection rules. All of the observed transition frequencies for the normal species were analyzed simultaneously using a two-top internal-rotation and rotation Hamiltonian. The potential barrier height V₃ to internal rotation of the methyl groups of the DMS was determined to be 745.5 (30) cm⁻¹. The transition frequencies observed for all the isotopomers were analyzed using an asymmetric-rotor rotational Hamiltonian, to determine rotational and centrifugal distortion constants. The r_s coordinates calculated from the observed rotational constants led to the conclusion that the CO moiety was located in a plane perpendicular to the skeletal plane of the DMS and bisecting its CSC angle. This structure of the CO-DMS is very much different from that of the CO-DME, in which the CO is located in the DME skeletal plane. The distance between the centers of gravity of the two moieties, R_cm, was calculated to be 3.789 Å for the CO-DMS, which is longer by only 0.11 Å than that in the CO-DME complex: 3.68 Å, in spite of the fact that the van der Waals radius of the S atom is much larger than that of the O atom. The small difference in R_cm is, in part, ascribed to the location of the CO relative to the DMS/DME. The more important reason is that the intermolecular bonding of the CO-DMS is stronger than that of CO-DME; by assuming a Lennard-Jones-type potential, the force constant of the van der Waals stretching mode and the dissociation energy were estimated to be 2.7 Nm⁻¹ and 3.3 kJ mol⁻¹, respectively, which were larger than those of the CO-DME: 1.4 Nm⁻¹ and 1.6 kJ mol⁻¹.     

Intensity,transition moment,and bandshapes for the second overtone of compressed CO

Infrared spectra of the CO second overtone absorption band have been studied for pressures up to 156 bar. The absolute intensity, obtained from direct measurements of the total band, is found to be (1.27 ± 0.04) × 10^-2cm^-2Am^-1 at 298 K. Using the vibrational moments for the ground state and the transitions 0–1 to 0–4, we have evaluated the coefficients M₀ to M₄ of the quartic dipole moment function for CO and the coefficients of the vibration-rotation interaction functions. The normalized 0–3 band contours of compressed CO were first generated by summing the pressure-broadened rotational lines with Lorentz profiles. A discrepancy appears between calculated and observed bandshapes and increases with density. An empirical model, which involves the sum of CO self-broadened lines with profile described as the product of a Lorentz function by a fitted exponential function, gives reasonable agreement with the experiments. The interference effects resulting from overlapping lines have been estimated within the impact approximation.     

The microwave spectrum and molecular conformation of peroxynitric acid (HOONO2)

The rotational spectrum of peroxynitric acid has been investigated in the 40- to 120-GHz region. The spectrum of the ground state is complicated by tunneling of the OH group, which causes a doubling of the asymmetric rotor spectrum. The magnitude of the tunneling splitting is such that it causes Coriolis interactions between the energy levels of the two tunneling states which lead to perturbations in the rotational spectrum. A combined analysis of the a- and b-type pure rotational transitions with the c-type tunneling transitions allows a perturbation-free determination of the rotational constants for the ground state. A similar analysis of the low-lying NO₂ torsional vibration at 145(6) cm⁻¹ has also been carried out. The dipole moments for each state have been determined by analysis of the second-order Stark effect. The molecular structure analysis indicates that all the heavy atoms are planar and only the hydrogen atom is out of the heavy atom plane. The preferred orientation of the hydrogen atom with respect to the plane of the heavy atoms is at an angle ∼106° with respect to the cis conformation.     

Rotational Spectra of Argon Acetone: A Two-Top Internally Rotating Complex

The rotational spectra of the argon acetone weakly bound complex was studied by pulsed jet Fabry-Perot Fourier transform microwave spectroscopy. Over 500 transitions of the complex were measured between 5.5 and 26 GHz from J=2-1 to J=12-11. The two methyl groups undergo hindered internal rotation resulting in four or five internal rotation states. The microwave transitions are within these states, resulting in a splitting of each rotational transition into four and sometimes five distinct transitions. The three-fold barrier to internal rotation is determined to be 260 cm⁻¹, 2% less than the 266 cm⁻¹ barrier in acetone itself. The structure of the complex has the argon atom above the heavy atom plane of the acetone, 3.52 Å from the CO bond and approximately in the C_s plane, which is perpendicular to the CCC plane of acetone.     

Millimeter-wave spectrum of Ne–CO: new measurements

The b-type rotational transitions of the van der Waals complex, Ne–CO have been measured using the intracavity OROTRON jet spectrometer in the frequency range of 80–115 GHz. The high sensitivity of this technique enabled us to detect all three Ne isotopic modifications of the complex, ²⁰Ne–CO, ²²Ne–CO, and ²¹Ne–CO in natural abundance. The observed and assigned transitions belong to the Q-branch of the K = 1–0 subband and include also R (0) and P (2) lines. The newly obtained data were analysed together with previously observed millimeter-wave b-type and microwave a-type rotational transitions.     

Accurate rotational constants of CO,HCl, and HF: Spectral standards for the 0.3- to 6-THz (10- to 200-cm−1) region

Accurate high-resolution spectroscopic measurements require secondary standards which can serve as convenient calibration references in laboratory and field research. We have measured the frequencies of a series of rotational transitions between 0.3 and 6 THz for several stable and readily obtainable gases (CO, HCl, and HF) to an accuracy better than one part in 10⁷ and present revised rotational constants for these molecules. The gases were selected (in part) due to their presence in the Earth's atmosphere in significant amounts and thus are convenient for the frequency calibration of atmospheric spectra.     

The high-resolution spectrum of ozone between 8 and 150 cm−1

The rotational spectrum of ¹⁶O₃ in the region 8–150 cm^?1 has been measured at high resolution (0.0033 cm^?1 at 30 cm^?1) with a polarizing FT interferometer. From the rotational analysis of the present data (about 1000 transitions) combined with the previously reported millimeterwave data (about 210 transitions), a new set of rotational and centrifugal distortion constants was derived, which reproduces the measured transition frequencies within their accuracy.     

Broadening of the R(0) and P(2) lines in the CO fundamental by helium atoms from 300 K down to 12 K: Measurements and comparison with close-coupling calculations

We present measurements of He-broadening parameters for the R(0) and P(2) lines in the fundamental band of ¹³CO at different temperatures between 12 K and room temperature. The broadening parameters are determined, taking into account confinement narrowing, by simultaneous least-squares fitting of spectra recorded using a frequency stabilized diode laser spectrometer. The pressure broadening cross sections are deduced and compared to close-coupling calculations and earlier results obtained for rotational transitions of ¹²CO.     

Microwave spectra and structure of an isoxazole-water complex

The rotational spectrum of a hydrogen-bonded isoxazole-water complex has been measured between 6–18 GHz with a pulsed nozzle Fourier transform microwave spectrometer. In addition to isoxazole-H₂O, the complexes with HDO and D₂O as well as isoxazole-¹⁵ N-H₂O have been investigated in order to determine the structure of the complex. Rotational constants, quartic centrifugal distortion constants and quadrupole coupling constants, where applicable, have been fitted to the measured transition frequencies of the isotopomers. Structural data, which have been deduced from the planar moments of inertia and the quadrupole coupling constants of the isotopomers, have established conclusively that water binds to nitrogen in the ring plane of isoxazole. Ab initio calculations have revealed that complexes with a hydrogen-bond to nitrogen or to oxygen are both stable. The complex with water attached to nitrogen has been found to be more strongly bound than that with water attached to oxygen. Small splittings of the rotational transitions of the two complexes with H₂O have been interpreted as being the result of an internal rotation of water with respect to isoxazole.     

The absorption spectrum of D<Subscript>2</Subscript>O in the region of 0.97 μm: the 3ν<Subscript>1</Subscript> + ν<Subscript>3</Subscript> vibrational–rotational band

The vibrational–rotational absorption spectrum of D₂O in the range from 10 120 to 10 450 cm^–1 is recorded on a Fourier transform spectrometer with a resolution of 0.05 cm^–1. The measurements were performed using a multipass White cell with an optical path length of 24 m. A light-emitting diode with brightness higher than that of other devices was used as a radiation source. The signal-to-noise ratio was about 10⁴. The spectrum is interpreted as consisting of lines of more than 400 transitions. The spectral characteristics of lines (centers, intensities, and half widths) are determined by fitting the Voigt profile parameters to experimental data by the least-squares method. The intensities of lines and the experimental rotational energy levels of the (301) vibrational state of the D₂ ¹⁶O molecule with high rotational quantum numbers are determined for the first time.     

Nuclear spin conversion in diatomic molecules

A mechanism of the internal interaction in dimers that mixes different nuclear spin modifications has been proposed. It has been shown that the intramolecular current associated with transitions between electronic terms of different parities can generate different magnetic fields on nuclei, leading to transitions between spin modifications and to the corresponding changes in rotational states. In the framework of the known quantum relaxation process, this interaction initiates irreversible conversion of nuclear spin modifications. The estimated conversion rate for nitrogen at atmospheric pressure is quite high (10^?3–10^?5 s^?1).     

Calculation of improved12C16O molecular constants and rotational-vibrational transition frequencies

We report the calculation of¹²C¹⁶O molecular constants and rotational-vibrational transition frequencies of the electronic ground state with improved accuracy. It is based on a recent paper containing results of accurate frequency measurements of a few CO lines. By using these data new rotational constants have been determined, they are then utilized to calculate band center frequencies of four bands. Futhermore, four vibrational constants were computed by means of the calculated band center frequencies. Tables of band center frequencies, andP andR branch transition frequencies are given for the bands 1–0 to 20–19. It was not possible to obtain standard deviations of line frequencies. It is shown, however, that the best molecular constants published lead to line frequencies with deviations of a few hundred MHz. Line frequencies calculated with the new molecular constants coincide exactly with frequencies measured. Finally, it is shown that there are pairs of transitions whose frequencies are close together. By measuring frequency differences of a number of such pairs it should be possible to further improve CO molecular constants.     

Millimeter-wave spectroscopy of weakly bound molecular complexes: Isotopologues of He-CO

Van der Waals complexes consisting of helium atoms and carbon monoxide molecules, He-¹²C¹⁶O, He-¹³C¹⁶O, He-¹²C¹⁸O, and He-¹³C¹⁸O are studied in the frequency range 110–140 GHz on an intracavity orotron-based spectrometer. Ten new lines, which correspond to rotational transitions and transitions to the bending vibration of the complex, are detected and identified as lines belonging to the R and P branches. The positions of the energy levels of isotopologue of the He-CO complex are refined by joint analysis of both the transition frequencies measured in this study and previously published microwave and infrared data. Isotopic dependences of the positions of the He-CO energy levels are obtained. These results can serve as the starting point for studying small helium clusters with embedded CO molecules.     

Population inversion on vibrational transitions of molecules under nonresonant optical excitation

The possibility of obtaining a population inversion on vibrational transitions of molecules through nonlinear effects when the pump radiation is absorbed in the wings of spectral lines is investigated theoretically. We show that a population inversion can be produced in molecules on vibrational transitions when intense pump radiation is absorbed in the blue wing of the R branch of the vibrational-rotational molecular spectrum. This effect is related to inequality of the probabilities of the absorption and stimulated emission of radiation and is attributable to collisional transitions between rotational levels. We have ascertained that the larger the rotational constant of the molecule and the higher the pump radiation intensity, the higher the effective frequency of the collisions that give rise to a population inversion. Using the carbon monoxide (CO) molecule as an example, we show that when intense (∼1010 W cm⁻²) pump radiation is absorbed in the blue wing of the R branch, a noticeable population inversion can be produced and the gain at the center of the R and P branches of the molecular spectrum can reach 0.011 and 0.250 cm⁻¹ at temperatures T = 300 and 100 K, respectively.     

The electron beam technique in carbon monoxide: Rotational transition probabilities

The electron beam fluorescence technique was developed to measure the rotational level population in the ground state of a carbon monoxide molecule. The data on rotational transition probabilities under ionization–excitation of CO (X¹Σ⁺) into the CO⁺ (B²Σ⁺) state by high energy electrons are presented, which noticeably differ from those predicted by the dipole excitation model. A flow in a free jet was used to obtain the experimental data in a low temperature rotationally equilibrium gas target. The probability matrix is represented in a compact form corresponding to the sudden approximation model.     

Monte Carlo scattering of sunlight by high altitude rocket plumes

A comprehensive model for the scattering of sunlight by high altitude rocket plumes is presented. The model consists of a Monte Carlo simulation of the multiple absorption-emission of solar photons by plume molecules. The physical and optical properties of high altitude plumes are discussed. It is shown that the expansion of rocket exhaust gases into a vacuum produces a highly nonequilibrium distribution of quantum state populations. As an example, the terminal translational and rotational temperatures for CO₂, for a 1 kN thrust engine, are predicted to be 10 and 15 K, respectively. Because these very low rotational temperatures result in a molecular absorption spectrum which consists of only several rotational lines, the optical opacity of both i.r. and u.v. transitions can be of order unity at large distances from the nozzle exit. For a 1 kN thrust engine, the centerline optical diameter equals unity at axial distances of approx. 10 m for CO₂ (4.3 μm) and 100m for CO (2,0) A → X. Detailed Monte Carlo calculations are presented for i.r. [CO₂(4.3 μm), H₂O (2.7 μm), and CO (4.6 μm)] and u.v. [H Lyα and CO A → X, B → X, C → X] transitions which demonstrate the dependence of scattered solar power on engine thrust, plume length and solar illumination angle. In general, plumes characterized by thrusts greater than 10 kN and lengths less than 0.1 km are optically opaque for i.r. transitions. However, u.v. transitions for H Lyα are quite optically thick even for a thrust as small as 1 kN and a plume length of 1 km. The u.v. transitions for CO can be optically opaque for 1 kN thrust and a plume length less than 1 km.     

Rotationally-Resolved Excitation Spectroscopy of the Methoxy Radical in a Supersonic Jet

Abstract

Laser-induced fluorescence excitation spectra of the methoxy radical have been obtained under sufficiently high resolution in a supersonic jet expansion. The rotational structure associated with its origin band has been identified in the midst of strong overlapping rotational transitions due to the hydroxyl radical in the 31490–31700 cm^?1 spectral region. Rotationally-resolved A ²A₁ - X ²E spectra of the 0₀ ⁰ band of methoxy have been explicitly assigned using the nomenclature for prolate symmetric top transitions in doublet states.     

Accurate intensity calibration for low wavenumber (−150 to 150 cm−1) Raman spectroscopy using the pure rotational spectrum of N2

We report on an accurate intensity calibration method for low wavenumber Raman spectroscopy. It uses the rotational Raman spectrum of N₂. The intensity distributions in the rotational Raman spectra of diatomic molecules are theoretically well established. They can be used as primary intensity standards for intensity calibration. The intensity ratios of the Stokes and anti‐Stokes transitions originating from the same rotational levels are not affected by thermal population. Taking the effect of rotation–vibration interactions appropriately into account, we are able to calculate these intensity ratios theoretically. The comparison between the observed and calculated ratios of the N₂ pure rotational spectrum provides an accurate relative sensitivity curve (error ~5 × 10⁻⁴) in the wavenumber region of −150 to 150 cm⁻¹. We determine the temperature of water solely from the low wavenumber Raman spectra, using a thus calibrated spectrometer. The Raman temperature shows an excellent agreement with the thermocouple temperature, with only 0.5 K difference. The present calibration technique will be highly useful in many applications of low wavenumber quantitative Raman spectroscopy. Copyright © 2015 John Wiley & Sons, Ltd.     

The infrared spectrum of the AsD radical in its XΣ state, recorded by laser magnetic resonance

The infrared spectrum of the AsD radical in the X³Σ⁻ ground state has been recorded using CO laser magnetic resonance. The radical was formed by the reaction between D atoms and arsenic powder. Low-N transitions in the fundamental band and in the (2-1) and (3-2) hot bands have been detected. Hyperfine structure from the ⁷⁵As nucleus (I = 3/2) is seen on many of the resonances. These measurements have been combined with information from previous measurements of rotational transitions at sub-millimeter wavelengths [H. Fujiwara, K. Kobayashi, H. Ozeki, S. Saito, A.I. Jaman, J. Chem. Soc. Faraday Trans. 93 (1997) 1045-1051] to determine an extended and improved set of molecular parameters for ⁷⁵AsD. Comparison is made with corresponding parameter values for AsH.