The pure rotational spectrum of TiS (XΔr) at submillimeter wavelengths

The pure rotational spectrum of TiS in its X³Δ_r ground state has been measured using millimeter-wave direct-absorption techniques in the frequency range of 313-425 GHz. This free radical was created by the reaction of titanium vapor, produced in a high-temperature Broida-type oven, with H₂S. Eight to ten rotational transitions were recorded for the main titanium isotopologue, ⁴⁸TiS, in the v = 0 and v = 1 levels, as well as for the v = 0 state of ⁴⁶TiS, observed in natural abundance (⁴⁸Ti:⁴⁶Ti = 74:8). All three Ω components were observed in almost every recorded transition, with no evidence for lambda-doubling. The data were fit with a Hund’s case(a) Hamiltonian, and rotational, spin-orbit, and spin-spin constants were determined, as well as equilibrium parameters for ⁴⁸TiS. Relatively few fine structure parameters were needed for the analysis of TiS (A, A_D, and λ), unlike other 3d metal species. The rotational pattern of the three fine structure components suggests the presence of a nearby excited ¹Δ state, lying ∼3000 cm⁻¹ higher in energy. From the equilibrium parameters, the dissociation energy for TiS was estimated to be ∼5.1 eV, in reasonable agreement with past thermochemical data.     

The pure rotational spectrum of ZnO in the XΣ and aΠi states

The pure rotational spectrum of ZnO has been measured in its ground X¹Σ⁺ and excited a³Π_i states using direct-absorption methods in the frequency range 239-514 GHz. This molecule was synthesized by reacting zinc vapor, generated in a Broida-type oven, with N₂O under DC discharge conditions. In the X¹Σ⁺ state, five to eight rotational transitions were recorded for each of the five isotopologues of this species (⁶⁴ZnO, ⁶⁶ZnO, ⁶⁷ZnO, ⁶⁸ZnO, and ⁷⁰ZnO) in the ground and several vibrational states (v = 1-4). Transitions for three isotopologues (⁶⁴ZnO, ⁶⁶ZnO, and ⁶⁸ZnO) were measured in the a³Π_i state for the v = 0 level, as well as from the v = 1 state of the main isotopologue. All three spin-orbit components were observed in the a³Π_i state, each exhibiting splittings due to lambda-doubling. Rotational constants were determined for the X¹Σ⁺ state of zinc oxide. The a³Π_i state data were fit with a Hund’s case (a) Hamiltonian, and rotational, spin-orbit, spin-spin, and lambda-doubling constants were established. Equilibrium parameters were also determined for both states. The equilibrium bond length determined for ZnO in the X¹Σ⁺ state is 1.7047 Å, and it increases to 1.8436 Å for the a excited state, consistent with a change from a π⁴ to a π³σ¹ configuration. The estimated vibrational constants of ω_e ∼ 738 and 562 cm⁻¹ for the ground and a state agreed well with prior theoretical and experimental investigations; however, the estimated dissociation energy of 2.02 eV for the a³Π_i state is significantly higher than previous predictions. The lambda-doubling constants suggest a low-lying ³Σ state.     

The rotational spectrum of the SH radical in its XΣ state

All the available data on the rotational energy levels of the SH⁺ (sulfoniumylidene) radical in the v = 0 and 1 levels of the X³Σ⁻ ground state have been subjected to a single, weighted least-squares fit to determine an improved set of molecular parameters for this molecule. The results have been used to calculate the rotational spectrum of the SH⁺ radical in the v = 0 and 1 levels up to the N = 4-3 transition.     

The sub-millimeter and Fourier transform microwave spectrum of HZnCl (X Σ)

The pure rotational spectrum of HZnCl (X ¹Σ⁺) has been recorded using sub-millimeter direct-absorption methods in the range of 439-540 GHz and Fourier transform microwave (FTMW) techniques from 9 to 39 GHz. This species was produced by the reaction of zinc vapor and chlorine gas with H₂ or D₂ in a d.c. glow discharge for the sub-millimeter studies. In the FTMW measurements, HZnCl was created in a discharge nozzle from Cl₂ and (CH₃)₂Zn. Between 5 and 10 rotational transitions were measured in the sub-millimeter regime for four zinc and two chlorine isotopologues; four transitions were recorded with the FTMW machine for the main isotopologue, each consisting of several chlorine hyperfine components. The data are consistent with a linear molecule and a ¹Σ⁺ ground electronic state. Rotational and chlorine quadrupole constants were established from the spectra, as well as an r_m⁽²⁾ structure. The Zn-Cl and Zn-H bond lengths were determined to be 2.0829 and 1.5050 Å, respectively; in contrast, the Zn-Cl bond distance in ZnCl is 2.1300 Å, longer by ∼0.050 Å. The zinc-chlorine bond distance therefore shortens with the addition of the H atom. The ³⁵Cl electric quadrupole coupling constant of eQq = −27.429 MHz found for HZnCl suggests that this molecule is primarily an ionic species with some covalent character for the Zn-Cl bond.     

Vibrational and rotational excitation effects of the N(2D) + D2(X1Σg +) → ND(X3Σ+) + D(2S) reaction

The effects of the rovibrational excitation of reactants in the N(²D) + D₂(X¹Σ_g⁺) → ND(X³Σ⁺) + D(²S) reaction are calculated in a collision energy range from the threshold to 1.0 eV using the time-dependent wave packet approach and a second-order split operator. The reaction probability, integral cross-section, differential cross-section and rate constant of the title reaction are calculated. The integral cross-section and rate constant of the initial states v = 0, j = 0, 1, are in good agreement with experimental data available in the literature. The rotational excitation of the D₂ molecule has little effect on reaction probability, integral cross-section and the rate constant, but it increased the sideways and forward scattering signals. The vibrational excitation of the D₂ molecule reduced the threshold and broke up the forward–backward symmetry of the differential cross-section; it also increased the forward scattering signals. This may be because the vibrational excitation of the D₂ molecule reduced the lifetime of the intermediate complex.     

Emission bands of AIH (X1Σ+): The 2-0 sequence

Seven bands of the 2-0 sequence of AlH in its X¹Σ⁺ ground state have been observed in emission from a carbon furnace and recorded with a Bomem interferometer. Improved values for the molecular constants have been obtained. The principal constants are B_e = 6.3937(4), α₃ = 0.1868(3), 10⁴D_e = 3.683(10), ω_e = 1682.43, and ω_eχ_e = 29.11 cm⁻¹, where the error limits are 3σ. Possibilities for observing AlH in astrophysical sources are discussed.     

The principle of primary spectrum pyrometry

1 Introduction Planck Law[1] is the fundamental of radiation temperature measurements, which in- dicates the quantitative relationship between the radiation intensity and the temperature of ideal blackbody.wherewhere C1 is Planck first constant, C2 Planck second constant, λ the wavelength, ε the spectral emissivity of an actual surface, I = ε (λ, T, θ, φ, β), Ib(λ, T) the radiation distri- bution of the real surface, λ1 the lower limit wavelength, λ2 the higher limit wavelength, d…     

The emission spectrum of the CΣ–XΣ system of AlH

The ultraviolet spectrum of AlH has been investigated at high resolution between 42 000 and 45 000 cm⁻¹ using a conventional spectroscopic technique. The AlH molecules were formed and excited in an aluminium hollow-cathode lamp with two anodes, filled with a mixture of Ne carried gas and a trace of NH₃. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. The 0–0, 1–1 and 1–2 bands of the C¹Σ⁺–X¹Σ⁺ transition have been identified and rotationally analyzed. The new data were elaborated with help of recent X¹Σ⁺ state parameters reported by White et al. [J. Chem. Phys. 99 (1993) 8371–8378] and by Szajna and Zachwieja [Eur. Phys. J. D. 55 (2009) 549–555]. Determined constants of the excited C¹Σ⁺ state include: T_e = 44 675.3711(57) cm⁻¹, ω_e = 1575.3357(42) cm⁻¹, ω_ex_e = [125.5] cm⁻¹, B_e = 6.66804(32) cm⁻¹, α_e = 0.55839(56) cm⁻¹, D_e = 2.23(13) × 10⁻⁴ cm⁻¹, β_e = 6.13(25) × 10⁻⁴ cm⁻¹ and r_e = 1.613132(39) Å. The C¹Σ⁺ state is found to be extensively perturbed in the v = 0 and 1 vibrational level at J = 20, 22 − 27 and J = 5 − 9, respectively. This was probably caused by the interaction with the vibrational levels of the outer minimum.     

State-to-state rotational energy transfer in OH (A 2Σ+, υ′=1)

State-to-state rotational energy transfer (RET) coefficients for thermal collisions of OH (A ²⁺, =1) with He, Ar, N₂, CO₂, and H₂O at 300K were determined from time-resolved laser-induced fluorescence (LIF) measurements. The RET coefficients are very similar in both qualitative behaviour and absolute magnitude to those measured previously for OH (A ²⁺, =0).     

Submillimeter-wave spectroscopy of VN (XΔr) and VO (XΣ): A study of the hyperfine interactions

The pure rotational spectra of VN (X³Δ_r) and VO (X⁴Σ⁻) have been recorded in the frequency range 290-520 GHz using direct absorption spectroscopy. These radicals were synthesized in the gas-phase from the reaction of VCl₄ with either N₂ or H₂O in an AC discharge. Seven rotational transitions were recorded for each molecule; in both sets of spectra, fine and hyperfine structures were resolved. The data sets for VN and VO were fit with Hund’s case (a) and case (b) Hamiltonians, respectively, and rotational, fine structure, and hyperfine constants determined. For VN, however, an additional hyperfine parameter, Δa, was necessary for the analysis of the Ω = 2 sublevel to account for perturbations from a nearby ¹Δ state, in addition to the usual Frosch and Foley constants. Determination of Δa suggests that the ¹Δ state lies ∼3000 cm⁻¹ above the ground state. In VO, the hyperfine structure in the F₂ and F₃ components was found to become heavily mixed due to an avoided crossing, predicted by previous optical studies to be near the N = 15 level. The hyperfine constants established for these two molecules are consistent with the proposed σ¹δ¹ and σ¹δ² electron configurations.     

The high-resolution spectrum of the ν1 (A1) band of 12CD3F

The spectrum of the ν₁ (A₁) band of ¹²CD₃F has been recorded with a resolution of 0.010 cm⁻¹ and deconvolved to 0.005 cm⁻¹. Over 1050 transitions have been assigned with K ≤ 16 and J ≤ 42. The spectrum is highly perturbed, exhibiting avoided crossings in most of the observed sub-bands. The origin of most of the local and global resonances has been determined and the coupling constants estimated. Due to the complexity of the spectrum resulting from the 24 potential interacting states in the region, the assigned frequencies were fitted in a restricted manner (K ≤ 3, J ≤ 15), to obtain the following effective constants for the band: ν₀ = 2090.8118(20) cm⁻¹, α^A = 1.19743 × 10⁻² cm⁻¹, and α^B = −1.8489 × 10⁻³ cm⁻¹. From an unrestricted least-squares analysis, fixing the above parameters the β's (D_v^x = D₀^x − β_v^x) were calculated to be β^J = 1.7776 × 10⁻⁷ cm⁻¹, β^JK = 8.3406 × 10⁻⁷ cm⁻¹, and β^K = −6.3829 × 10⁻⁷ cm⁻¹. These constants serve as good starting parameters for the global analysis necessary to fully analyze the 5-μm region of the ¹²CD₃F spectrum.     

The B 2Σ+–X 2Σ+ Transition of 12C17O+: The 2‐υ″ Progression

Abstract

Three new bands of the B ²Σ⁺–X ²Σ⁺ system of ¹²C¹⁷O⁺ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the ¹⁷O₂ isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of ¹²C¹⁷O⁺ are ω_e=2185.9658(84), ω_e x _e = 14.7674(11), B _e=1.927001(38), α_e=1.8236(22)×10^?2, γ_e=?0.331(28)×10^?4, D _e=6.041(12)×10^?6, β_e=0.100(31)×10^?7 cm^?1, and the equilibrium constants for the excited state are σ_e=45876.499(15), ω_e=1712.201(12), ω_e x _e=27.3528(39), B _e=1.754109(35), α_e=2.8706(57)×10^?2, γ_e = ?1.15(19)×10^?4, D _e=7.491(20)×10^?6, β_e=2.13(12)×10^?7, γ_e = 2.0953(97)×10^?2, and α_γe=?9.46(59)×10^?4 cm^?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B ²Σ⁺ and X ²Σ⁺ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the B–X system.     

The rotational spectrum of chlorine nitrate (ClONO2) in the four lowest nν9 polyads

The analysis of the recently recorded 78-378 GHz broadband spectrum of ClONO₂ has been extended to cover rotational transitions in all 14 excited vibrational states up to 650 cm⁻¹ above the ground state. We report new measurements and analysis of the 2ν₉ and 3ν₉ dyads, and first assignment and analysis for the 4ν₉ and 5ν₉ triads. The polyad fits encompass a total of over 20 000 newly measured transition frequencies and spectroscopic constants are reported for 10 vibrationally excited states in each of ³⁵ClONO₂ and ³⁷ClONO₂. All polyads were fitted with a new coupling scheme between the perturbing states combining c-axis Coriolis and Fermi interactions. The scheme is validated by multiple tests of the physical significance of the derived parameters and it results in improved deviations of fits and significant reduction in the number of adjustable parameters.     

The near infrared (0.8−2.6µm) absorption spectrum of a dense sodium vapor and possible mechanisms of the spectrum formation

The absorption coefficient of a dense sodium vapor (N₀ ～ 10¹⁷–10¹⁸ cm^{? 3}) in the near infrared spectral range (0.8–2.6 µm) was measured in a homogeneously heated isolated cell. In the range of parameters studied, the sample exhibits significant absorption. Neither the observed spectral features nor the measured absorption coefficients can be explained using the existing notions of the possible absorption mechanisms (absorption due to a forbidden intercombination transition, collision-induced processes, the trimer vapor component, and many-particle effects) and the available data.