Sub-doppler saturation spectroscopy of HCN up to 1 THz and detection of J = 3 → 2 (4 → 3) emission from TMC1

Abstract

Very high-resolution (∼ 30 kHz) and very precise (±2 kHz) saturation dip and crossover dip measurements are reported for HCN. Nine consecutive rotational transitions of the vibrational ground state were recorded, covering the rotational spectrum up to the J = 11 ← 10 transition at 975 GHz. Commencing the saturation dip measurements with the J = 3 ← 2 transition located at 265 886.4 MHz, all rotational transitions were measured up to J = 11 ← 10 (ΔF = 1), positioned at a center frequency of 974 487.2 MHz. It has become possible to resolve the hyperfine structure of every rotational transition to varying degrees. Transitions obeying the selection rules ΔJ = 1, ΔF = 0 are have been resolved, those obeying the selection rules J = 1, F = 1 are only resolved for transitions lower than the J = 6 ← 5 transition. These new experimental saturation dip data, together with the molecular beam maser emission data of the J = 1 → 0 and J = 2 → 1 transitions reported by De Lucia and Gordy, (Phys. Rev. 187, 58 (1969)), and the recent terahertz measurements performed in this laboratory up to J = 22-21 at 1.946 THz (Maiwald et al., J. Mol. Spectrosc. 202, 166 (2000)), were subjected to a least squares analysis which yielded a highly precise set of molecular constants for the ground state of HCN: B = 44 315.974 970 (156) MHz, D = 0.087 216 35 (169) MHz, H = 0.086 96 (242) Hz; eQq = -4.709 03 (162) MHz, eQqJ = 0.244 (88) Hz, CN = 10.09 (38) kHz, CNJ = -0.0143 (86) mHz. Two constants, the hydrogen spin-rotation, CH = -4.35 (5) kHz, and the spin-spin interaction between the proton and nitrogen nucleus, SNH = 0.154 (3) kHz, can not be determined from the saturation dip measurements and have been taken from Ebenstein and Muenter, J. Chem. Phys. 80, 3989 (1984). There also a value for the ground state permanent electric dipole moment (in Debye's) is given, which we quote for completeness: 〈μ〉000 = 2.985 188 (3) D. We also report the discovery of the J = 3 → 2 and J = 4 → 3 ground state rotational transitions of HCN in the dark, cold molecular cloud TMCl by using the KOSMA 3m-Submillimeter Telescope located in the central Swiss Alps. For the J = 3 → 2 transition the hyperfine splitting has partly been resolved. The intensities of the hyperfine components are anomalous, and they are not in thermodynamic equilibrium.