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Register a new userThe rotational spectrum of $^{15}$ND. Isotopic-independent Dunham-type analysis of the imidogen radical
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The rotational spectrum of $^{15}$ND in its ground electronic $X^{3}Sigma^{-}$ state has been observed for the first time. Forty-three hyperfine-structure components belonging to the ground and v = 1 vibrational states have been recorded with a frequency-modulation millimeter-/submillimeter-wave spectrometer. These new measurements, together with the ones available for the other isotopologues NH, ND, and $^{15}$NH, have been simultaneously analysed using the Dunham model to represent the ro-vibrational, fine, and hyperfine energy contributions. The least-squares fit of more than 1500 transitions yielded an extensive set of isotopically independent $U_{lm}$ parameters plus 13 Born--Oppenheimer Breakdown coefficients $Delta_{lm}$. As an alternative approach, we performed a Dunham analysis in terms of the most abundant isotopologue coefficients $Y_{lm}$ and some isotopically dependent Born--Oppenheimer Breakdown constants $delta_{lm}$ [R. J. Le Roy, J. Mol. Spectrosc. 194, 189 (1999)]. The two fits provide results of equivalent quality. The Born--Oppenheimer equilibrium bond distance for the imidogen radical has been calculated [$r_e^{BO}$ =103.606721(13) pm] and zero point energies have been derived for all the isotopologues.
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The deuteration mechanism of molecules in the interstellar medium (ISM) is still being debated. Observations of deuterium-bearing species in several astronomical sources represent a powerful tool to improve our understanding of the interstellar chemistry. The doubly deuterated form of the astrophysically interesting Amidogen radical could be a target of detection in space. In this work, the rotational spectrum of the ND$_{2}$ radical in its ground vibrational and electronic $X^{2}B_{1}$ states has been investigated between 588 and 1131 GHz using a frequency modulation millimeter/submillimeter-wave spectrometer. The ND$_{2}$ has been produced in a free-space glass absorption cell by discharging a mixture of ND$_{3}$ and Ar. Sixty-four new transition frequencies involving $J$ values from 2 to 5 and $K_{a}$ values from 0 to 4 have been measured. A global analysis including all the previous field-free pure rotational data has been performed, allowing for a more precise determination of a very large number of spectroscopic parameters. Accurate predictions of rotational transition frequencies of ND$_{2}$ are now available from a few GHz up to several THz.
Methyl mercaptan (CH3SH) is a known interstellar molecule with abundances high enough that the detection of some of its minor isotopologues is promising. The present study aims at providing accurate spectroscopic parameters for the (13)CH3SH isotopologue to facilitate its identification in the interstellar medium at millimetre and submillimetre wavelengths. Through careful analysis of recent CH3SH spectra from 49-510 GHz and 1.1-1.5 THz recorded at natural isotopic composition, extensive assignments were possible not only for the ground torsional state of (13)CH3SH, but also in the first and second excited states. The torsion-rotation spectrum displays complex structure due to the large-amplitude internal rotation of the (13)CH3 group, similar to the main and other minor isotopic species of methyl mercaptan. The assigned transition frequencies have been fitted to within experimental error with a 52-parameter model employing the RAM36 programme. With predictions based on this fit, (13)CH3SH was searched for in spectra from the Atacama Large Millimetre/submillimetre Array (ALMA) towards the Galactic centre source Sgr B2(N2). Several transitions were expected to be observable, but all of them turned out to be severely blended with emission from other species, which prevents us from identifying (13)CH3SH in this source.
Transient diode laser absorption spectroscopy has been used to measure three strong vibronic bands in the near infrared spectrum of the C$_2$H, ethynyl, radical not previously observed in the gas phase. The radical was produced by ultraviolet excimer laser photolysis of either acetylene or (1,1,1)-trifluoropropyne in a slowly flowing sample of the precursor diluted in inert gas, and the spectral resolution was Doppler-limited. The character of the upper states was determined from the rotational and fine structure in the observed spectra and assigned by measurement of ground state rotational combination differences. The upper states include a $^2Sigma ^+$ state at 6696 cm$^{-1}$, a second $^2Sigma ^+$ state at 7088 cm$^{-1}$, and a $^2Pi$ state at 7110 cm$^{-1}$. By comparison with published calculations (R. Tarroni and S. Carter, textit{J. Chem. Phys} textbf{119}, 12878 (2003) and textit{Mol. Phys}. textbf{102}, 2167 (2004)), the vibronic character of these levels was also assigned. The observed states contain both $X^2Sigma^+$ and $A^2Pi$ electronic character. Several local rotational level perturbations were observed in the excited states. Kinetic measurements of the time-evolution of the ground state populations following collisional relaxation and reactive loss of the radicals formed in a hot, non-thermal, population distribution were made using some of the strong rotational lines observed. The case of C$ _{2} $H may be a good place to investigate the behavior at intermediate pressures of inert colliders, where the competition between relaxation and reaction can be tuned and observed to compare with master equation models, rather than deliberately suppressed to measure thermal rate constants.
Frequency-modulated diode laser transient absorption spectra of the ethynyl radical have been recorded at wavelengths close to 1.66 $mu$m. The observed spectrum includes strong, regular, line patterns. The two main bands observed originate in the ground $tilde{X},^2Sigma^+$ state and its first excited bending vibrational level of $^2Pi$ symmetry. The upper states, of $^2Sigma^+$ symmetry at 6055.6 cm$^{-1}$ and $^2Pi$ symmetry at 6413.5 cm$^{-1}$, respectively, had not previously been observed and the data were analyzed in terms of an effective Hamiltonian representing their rotational and fine structure levels to derive parameters which can be used to calculate rotational levels up to J = 37/2 for the $^2Pi$ level and J = 29/2 for the $^2Sigma$ one. Additionally, a weaker series of lines have been assigned to absorption from the second excited bending, (020), level of $^2Sigma$ symmetry, to a previously observed state of $^2Pi$ symmetry near 6819 cm$^{-1}$. These strong absorption bands at convenient near-IR laser wavelengths will be useful for monitoring CCH radicals in chemical systems.
The pure rotational transitions of the protonated hydrogen cyanide ion, HCNH+, and its isotopic species, HCND+ and DCND+, were measured in the 107 - 482 GHz region with a source modulated microwave spectrometer. The ions were generated in the cell with a magnetically confined dc-glow discharge of HCN and/or DCN. The rotational constant B0 and the centrifugal distortion constant D0 for each ion were precisely determined by a least-squares fitting to the observed spectral lines. The observed rotational transition frequencies by laboratory spectroscopy and the predicted ones are accurate in about 30 to 40 kHz and are useful as rest frequencies for astronomical searches of HCNH+ and HCND+.
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