Vibration-rotation bands of nitrous oxide: 4.1 micron region

The infrared spectrum of nitrous oxide has been measured and analyzed from 2265 cm^?1 to 2615 cm^?1. Newly refined effective rotational constants for twenty-one vibrational states of ¹⁴N₂O, three vibrational states each of ¹⁴N₂¹⁸O and ¹⁵N¹⁴N¹⁶O, two states of ¹⁴N¹⁵N¹⁶O and one state of ¹⁴N₂¹⁷O have been calculated.The most interesting features observed are two Δ-Σ “forbidden” bands, 04^2c0-00⁰0 and 12^2c0-00⁰0. These bands occur because of Coriolis interaction between unperturbed vibrational states having l = 0 and l = 2.     

Millimeter-Wave Spectroscopy of ClBS: An Improved Evaluation of the Equilibrium Structure of Chlorothioborine

The rotational spectrum of the unstable ClBS molecule has been investigated in the millimeter-wave region, from 80 to 195 GHz. A high-temperature reaction between crystalline boron and disulfur dichloride vapor was used to produce the molecule in a flow pyrolysis system. Eight different isotopic species were studied measuring lines in the ground and excited vibrational states 01¹0 (ClBS bend), 10⁰0 (ClB stretch), 02⁰0, 02²0, and 00⁰1 (BS stretch). The analysis of the spectra has been performed taking simultaneously into account both the Fermi resonance between the 10⁰0 and 02⁰0 states, and l-type resonance effects in the v₂=2 vibrational state. This procedure allowed us to calculate directly deperturbed rotational constants, from which the equilibrium rotational constant of seven isotopic variants could be accurately determined yielding a much improved evaluation of the equilibrium structure of chlorothioborine: r_e(ClB)=1.6806±0.0001 Å and r_e(BS)=1.6049±0.0001 Å. The equilibrium structures of ClBS and of the related molecules HBS, FBS, HCP, FCP, and ClCP have been also theo-retically evaluated by high-level CCSD(T) calculations performed using cc-pVTZ, cc-pVQZ, and cc-pV5Z basis sets. The different trends respectively observed for the BS and CP bond lengths in the XBS and XCP triatomic molecules are discussed.     

Determination of the vibrational temperature of OCS in a supersonic free jet

The rotational temperature of OCS in the v₂ = 1 excited state and the vibrational temperature in supersonic free jets seeded in Ar were measured by a diode-laser spectrometer. From the hot band associated to the ν₁ band, the rotational temperature in the v₂ = 1 state was obtained to be 5.7 K and the vibrational temperature obtained for this state was 213 K.     

The pure rotational Raman spectrum of CS2 in the ground and 010 vibrational states

The pure rotational Raman spectra of CS₂ in the 00⁰0 and 01¹0 vibrational states have been observed using a low power HeNe laser (λ = 6328 Å) and a high resolution plane grating spectrograph. The ΔJ = 2 transitions with J = odd in the 01¹0 state are clearly resolved from the ground state transitions thus allowing the determination of some upper state rotational constants. The molecular constants determined in this work are for the 00⁰0 ground state, B_00⁰0 = 0.10912 ± 0.7 × 10⁻⁵ cm⁻¹, (D_J)_00⁰0 = (0.83 ± 0.18) × 10⁻⁸ cm⁻¹ and for the 01¹0 excited state B_01¹0^c = 0.10935 ± 0.00002 cm⁻¹ and (D_J)_01¹0^c = (1.5 ± 0.6) × 10⁻⁸ cm⁻¹.     

Collisional broadening and shifting of OCS rotational spectrum lines

Broadening and shifting of carbonyl sulfide (OCS) rotational spectrum lines by pressure of N₂, O₂ and OCS were accurately studied in the frequency range 24–850 GHz at room temperature using a spectrometer with radio-acoustic detection of absorption. Rotational dependences of collisional widths of OCS spectrum lines were determined by a simple empirical polynomial fit of experimental data. Experimental uncertainties were analyzed. Results of supplementary test measurements of self-broadening of rotational OCS lines in the ν₂ excited vibrational state and carbon monoxide (CO) lines in the ground vibrational state are presented. Comparison of the obtained results with previously known measurements and theoretical calculations is given. The performed work allows for the first time development of accurate gaseous etalon of absorption for atmospheric applications and laboratory use, covering continuously the whole millimeter- and submillimeter-wave range.     

Laser Stark spectroscopy of FCN

Using a CO₂ laser, Stark shifted resonances have been measured for the CF stretching fundamental (ν₃) of FCN near 9.3 μm, and for two nearby “hot” bands. The band centers measured are 1076.492007 ± 0.000013 cm^?1 for 00⁰1-00⁰0, 1085.741046 ± 0.000050 cm^?1 for 01¹1-01¹0, and 1091.16222 ± 0.00015 cm^?1 for 02⁰1-02⁰0. The ground state dipole moment of FCN is found to be 2.1203 ± 0.0010 D and dipole moments are also given for the other states observed. Values are given for the rotational constant and l-doubling constant for the 01¹1 state.     

Rotational relaxation of the 0001 level of CO2 including radiative transfer in the 4.3-μm band of planetary atmospheres

Accurate numerical solutions have been obtained for a model problem of rotational relaxation within the 00⁰1 vibrational level of C¹²O₂¹⁶ accounting for the transfer of radiation in the lines of the fundamental transition 00⁰1-00⁰0 of the 4.3-μm band. Intramolecular exchange of vibrational energy with the reservoir of v₂ quanta and absorption of solar radiation in the 00⁰1- 00⁰0 band are accounted for. A plane-parallel isothermal atmosphere of pure CO₂ with the barometric pressure distribution and solar illumination is assumed. The line opacity is represented by nonoverlapping Voigt profiles depending on temperature and pressure. The transfer problem, which is equivalent to that of a multiplet with a large number of lines with a common lower level, was solved by a generalization of the Rybicki method. We find significant deviations from ratational LTE (local thermodynamic equilibrium) in regions in which the harmonic average of the optical depth over the band is of order 10³-10⁴. Absorption of solar radiation can affect significantly the source functions of lines at the centers of the P and R branches. Deviations from rotational LTE are shown to influence the intensity and shape of the 4.3-μm band of CO₂ in the spectra of Mars and Venus, and should be taken into account in the interpretation of the observations in which the rotational structure is resolved, especially in limb measurements, where these effects are particularly apparent.     

The millimeter-wave rotational spectrum of CF3CCD in the excited vibrational state v10=2

The millimetre-wave rotational spectra of the excited vibrational state v₁₀=2 of the symmetric top molecule, CF₃CCD, have been recorded for J^′′=12 up to J^′′=25. The l=±2 and l=0 series have been assigned and the spectra analysed to give rotational parameters including x_ll=7716.975 MHz. The main interactions between states of different l are the r_t(2,−1)=0.158 MHz and q_t⁺(2,2)=3.308 MHz. Two type of l-resonance are identified, one of which is due to an avoided crossing between the l=0 and l=+2 series. The spectra are qualitatively similar to the corresponding ones of CF₃CCH.     

CO2 laser saturation Stark spectra and global rovibrational analysis of the main isotopic species of carbonyl sulfide (OC34S,O13CS,and 18OCS)

Stark spectra of OC³⁴S, O¹³CS, and ¹⁸OCS have been recorded with an intracavity CO₂ laser spectrometer. The observed transitions are the 2ν₂ band and the associated hot bands from ν₂¹, ν₁, 2ν₂⁰, 2ν₂², ν₁ + ν₂¹, 3ν₂¹, and 3ν₂³. One line has also been observed in the 00⁰1 ← 02⁰0 band of OC³⁴S. For each isotopic species of OCS, a global weighted least-squares analysis has been applied simultaneously on all available zero-field and Stark data, yielding coherent sets of rovibrational and electrical molecular parameters. From the equilibrium rotational constants we have deduced an improved equilibrium structure for the OCS molecule.     

The 2ν1 + ν3 and 3ν3 bands of 14N16O2

The spectra of the 2ν₁ + ν₃ and 3ν₃ bands of ¹⁴N¹⁶O₂ have been recorded by means of high-resolution Fourier transform spectroscopy and have been extensively analyzed. The (2 0 1) and (0 0 3) rotational levels deduced from the analysis have been reproduced within the experimental uncertainty using a Hamiltonian which takes into account the Coriolis interaction coupling the vibrational states of the diads {(2 2 0), (2 0 1)} and {(0 2 2), (0 0 3)}. Finally, precise sets of vibrational energies, and spin-rotation, rotational, and coupling constants have been derived for these vibrational states.     

The oscillator strength of theC 2 Swan bands

Litetimes of six individual rotational levels in theν=0 vibrational level of the³ π _g state of C₂ were measured by monitoring the fluorescent decay after pulsed laser excitation. A value of 92±5 ns was obtained, 25% lower than previous measurements. The corresponding oscillator strength for the Swan (0-0) band isf ₀₀=0.032±0.002, in agreement with recent theoretical work.     

M-dependence of collisional transfer of rotational energy in OCS mixtures

Collision-induced transitions between rotational levels of OCS in the ground vibrational state have been investigated by steady-state microwave double resonance, with the M sublevels separated by a Stark field. The (2 ← 1)_P-(1 ← 0)_S, (3 ← 2)_P-(1 ← 0)_S, and (4 ← 3)_P-(1 ← 0)_S systems have been studied for pure OCS and for mixtures with excess CH₃OH, He, and H₂. For four-level systems having dipolar connections (ΔJ = 1; ΔM = 0, ± 1; parity ± ? ?) between pump and signal levels, it is found for OCS and the OCS-CH₃OH mixture that the dipole-type ΔJ = 1 transitions always dominate the collisional transfer, but for the OCS-He and OCS-H₂ mixtures that ΔJ = 2 quadrupole-type transitions are dominant. For all four collision partners, significant ΔJ = 2 and ΔJ = 3 collisional transfer is observed in some systems, indicating the presence of high-order terms in the collisional interaction.     

Millimeterwave spectrum of DC discharge produced ICN in excited vibrational states

An indigenously built 50 kHz source-modulated millimeter-wave spectrometer was used to produce cyanogen iodide (ICN) in the excited vibrational states (01¹0), (03³0), (10⁰0), (20⁰0) and (02⁰0) and record their corresponding rotational spectra. The analysis of the recorded spectra was carried out in the frequency range of 57.0–98.0 GHz. ICN was produced using a DC glow discharge through a mixture of methyl iodide (CH₃I) and benzyl cyanide (C₆H₅CH₂CN) vapor at low pressure. ¹²⁷I nuclear quadrupole hyperfine structure and the l-type doublet spectra of (01¹0) state have been resolved. The observed and assigned rotational transition frequencies were used in a least-square fit to determine more accurate values of molecular constants. The agreement between the derived parameters and those reported earlier clearly indicate that the reported spectral lines belong to ICN in the excited vibrational states. It also indicates that ICN could be produced in selective excited vibrational states by DC glow discharge technique.     

Energy transfer processes in linear triatomic molecule-solid surface collisions

The semiclassical stochastic trajectory method is extended to the study of rotational and vibrational transitions for linear triatomic molecules colliding with non-rigid solid surfaces. Rotational and vibrational motion are treated by quantum mechanics, translational motion by classical mechanics, and surface atom motion by the classical generalized Langevin equation. Self-consistent coupling of all motions is enforced via Ehrenfest's theorem. Calculations of the kinetic energy and gas temperature dependence of trapping probabilities, vibrational relaxation probabilities and final vibrational state distributions are presented for the CO₂-Ag(111) system at surface temperatures of 0 and 600 K. The trapping probabilities are greatly enhanced by the rotational motion and also vary to some degree with the initial vibrational state of the CO₂. Total vibrationally inelastic probabilities are on the order of 10⁻² for a single collision event with an initial state (00°1). For the initial state (01¹0) these are much larger, ~ 10⁻¹, due to the nature of bending mode motion. In conjunction with the large trapping probabilities, the mechanism of vibration to vibration, rotation, translation, phonon energy transfer can provide vibration relaxation probabilities in the range of those measured experimentally. A pseudo-selection rule for conservation of vibrational angular momentum is found.     

Microwave spectra of CH314NC and CH315NC in the 4ν8 state

The J → J + 1 transitions (J = 4, 5, 6, 7, 8) in the microwave spectra of methyl isocyanide and its ¹⁵N derivative have been obtained and analyzed in the 4ν₈ degenerate vibrational state. Theoretical analytical expressions are given for the rotational frequencies in a 4ν_E state, separately for the l = 0, ±2, ±4 values. These formulas could only be used as a starting point for the assignment and analysis, because of the complexity of the spectrum and the number of accidental resonances appearing in many l = 0 and ±2 lines for low K values. A detailed analysis was obtained through a diagonalization of the energy matrix. Many types of A₁A₂ doublings could be localized; in particular for CH₃¹⁵NC the K, l = ±1, ±4 doubling allowed the calculation of the g₆ coefficient of the 〈K, l|H|, l ± 6〉 term. As in the 3ν₈ state, some lines seem to undergo the effects of a vibrational resonance. A set of constants is given for both species, and a comparison is made with the other states.     

The rotational spectra of the 79, 69, and 7 vibrational states of nitric acid

The rotational spectra of the first three vibrational states of nitric acid above 1000 cm⁻¹, 7¹9¹, 6¹9¹, and 7², have been measured and analyzed. The 7² state, along with the previously published 7¹ state, show the rotational and centrifugal distortional constants have a near linear dependence on the υ₇ vibrational quantum number. Large changes for several centrifugal distortion constants of the υ₇ = n series of states are attributed to a c-type Coriolis resonance manifold between the ν₇ and ν₆ vibrational modes and the Hamiltonian reduction and representation used to fit the spectra. The 7¹9¹ and 6¹9¹ states have torsional splittings of 12.361(8) and 22.47(1) MHz, respectively. These splittings are large compared to 2.340(8) MHz of the 9¹ state and can be explained by a ∼1-2% mixing through anharmonic Fermi resonances with the 9³ state, which has a large torsional splitting of ∼1760 MHz. The millimeter/submillimeter-wave spectrum of each state was fit separately to the experimental uncertainty of the measurements. The resultant rotational constants, distortional constants and inertial defects agree well with DFT calculations.     

The Rotational Spectrum of SiHF3 in the Vibrational State υ6=2: Observation of Direct l-Type Resonance Transitions

The υ₆=2 vibrational state of the main isotopomer of trifluorosilane, ²⁸SiHF₃, has been investigated in the centimeter- and millimeter-wave ranges. Rotational spectra following the Δ J=1, Δk=Δ l=0 selection rule have been measured up to J=24 and K=23 and for both values of ∣l∣. Two types of direct l-type resonance transitions induced by the (Δ l=Δk=±2) interaction could be observed by means of waveguide Fourier transform microwave spectroscopy in the range 8-26 GHz: 252 transitions following the Δ J=0, Δl=Δk=±2 selection rule covering values of J=7-39 and G=∣k-l∣ from 1 to 18 and 90 transitions following the Δ J=0, Δl=Δ k=±4 selection rule covering values of J=17-52 and G from 1 to 4. Due to the strong (2,2) resonance, 18 A₁-A₂ splittings of the k=l=±2 states from J=36-53 could also be observed. Accidental near-degeneracies lead to strong perturbations due to Δ (k-l)=±3 interactions, enabling the observation of perturbation-allowed transitions with selection rules k=±3(l=±2)↔±4(±2), ±2(±2), A₊↔ ±1(?2), A₋ and ± 1(0)↔± 6(±2). In a multiple-fit analysis the experimental data have been refined using five reduced forms of the effective Hamiltonian as proposed by Sarka and Harder [J. Mol. Spectrosc.197, 254-261 (1999)]. Parameters up to seventh order have been determined including the axial rotational constant C for both values of ∣l∣ and the vibrational separation of the ∣l∣=0 and 2 states. The unitary equivalence of the determined parameter sets has been demonstrated up to fifth order. Differences of the rotational constants in the various parameter sets have been explained by the theory of reduction. Sign relations of the fitted parameters and general features of the direct l-type resonance spectrum in a υ_t=2 level are discussed.     

Lifetime Measurements of the DΠ State of HfS and the bΠ1 State of HfO

Lifetime measurements of individual rotational levels in excited states of hafnium oxide and hafnium sulfide have been performed using population probing by resonant two-photon ionization in a molecular beam. For the b³Π₁ state of HfO rotational levels in the vibrational level v=0 were found to have lifetimes in the region 650-700 ns. For the D¹Π state of HfS rotational level lifetimes in the vibrational levels v=0 and v=1 were determined to be around 240 ns. The technique used here provides very accurate results and the uncertainty in the reported values is only about 2%. Possible sources of errors are examined. The absorption oscillator strengths from the ground state are calculated.     

The 2ν2 band of 14N 16O2

The 2ν₂ band of ¹⁴N ¹⁶O₂ has been observed for the first time in the infrared, leading to precise energies for the K_a = 0, 1, 2 rotational levels of the (0 2 0) vibrational state. These levels have been reproduced within the experimental uncertainty using a Hamiltonian which takes into account the Coriolis interactions between (0 2 0) and (0 0 1) and between (1 0 0) and (0 0 1). In this way a precise band center ν₀ = 1498.3474 ± 0.0016 cm⁻¹ has been determined as well as improved rotational and coupling constants.     

Rotational and vibrational temperatures of electronically excited BiN radicals in a chemiluminescent flame

Rotational and vibrational temperatures of electronically excited BiN radicals in a low-pressure Bi_x+N/N₂*/N₂+Ar chemiluminescent flame have been deduced from high-resolution Fourier-transform emission spectra. Bands of three electronic transitions, a³Σ⁺(a₁1)→X¹Σ⁺(X0⁺), b⁵Σ⁺(b₁0⁺)→X¹Σ⁺(X0⁺), and b⁵Σ⁺(b₁0⁺)→a ³Σ⁺(a₁1), were analysed to determine the optical temperatures in the a³Σ⁺(a₁1) and b⁵Σ⁺(b₁0⁺) states. The rotational temperatures characterising the rotational populations in the a₁1, v=0 and 1 states were determined from the a₁→X, 0-2, 0-3, 0-4, 1-1, and 1-2 bands. The b₁→X, 0-8 and 0-11 bands, and the b₁→a₁, 0-0 bands served to determine the rotational temperature of the radicals in the b₁0⁺, v=0 state. The temperatures derived from the various bands and transitions were well consistent and the mean rotational temperature was determined to be 353±18 K, which is close to the translational temperature of the gas.Vibrational temperatures of the radicals in the a₁1 and b₁0⁺ states were derived from band intensities of the a₁→X and from the b₁→X as well as b₁→a₁ systems, respectively. The Franck-Condon factors needed were calculated with RKR potentials deduced from literature values of the rotational and vibrational constants in the three states involved. The a₁1 vibrational temperature (336±21 K) was close to the rotational temperature, while the b₁0⁺ vibrational temperature (438±36 K) differed, likely due to the previously observed perturbation of the b₁0⁺ state.