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Terahertz absorption spectroscopy was employed to extend the measurements on the pure rotational transitions of N 2 H + , N 2 D + and their 15 N-containing isotopologues in the ground state and first excited vibrational states for the three fundamental vibrational modes. In total, 91 new pure rotational transitions were observed in the range of 0.7–2.7 THz. The observed transition frequencies were fit to experimental accuracy, and the improved molecular parameters were obtained. The new measurements and predictions reported here will support the analysis of high-resolution astronomical observations made with facilities such as SOFIA and ALMA where laboratory rest frequencies with uncertainties of 1 MHz or smaller are required for proper analysis of velocity resolved astrophysical components.

We extended the measurements of the rotational transitions of D 2 H + up to 3 THz by using the JPL frequency multiplier chains and a TuFIR system at Toyama. D 2 H + was generated in an extended negative glow discharge cell cooled to liquid nitrogen temperature. We observed five new THz lines. All the available rotational transition frequencies together with the combination differences derived from the three fundamental bands were subject to least square analysis to determine the molecular constants. New THz measurements are definitely useful for better characterization of spectroscopic properties. The improved molecular constants provide better predictions of other unobserved rotational transitions.

In this paper, we report 30 THz measurements of ammonia in its excited, ν2 = 1, inversion state. These measurements include transition frequencies and pressure shifts (where significant enough to be observed). Included in the data are two forbidden and three ro-inversion transitions, as well as 18 transitions never directly measured before. The measurements were made with an all-solid-state, diode-laser, difference-frequency spectrometer. Using an innovative laser-frequency locking scheme, this spectrometer provided accurately determined and continuously tuned THz-frequencies without requiring accurate knowledge of the absolute laser frequencies. The details of the spectrometer’s frequency calibration is discussed. A global analysis of NH3 based on the available ground state, ν2 = 1 state, and ν2-band transitions was carried out, and the resulting set of recommended molecular effective-Hamiltonian parameters for ammonia is presented. In addition, calculated center frequencies and intensities for all possible transitions up to J = 20 between rotation, inversion, and vibration levels in the ground and ν2 = 1 states are included as supplementary material .

The rotation–torsion spectrum of the asymmetric frame-asymmetric top internal rotor propargyl alcohol (HCCCH 2 OH) has been extended into the millimeter and submillimeter wave spectral regions. Over 2000 ground torsional state transitions have been measured and analyzed up to rotational quantum numbers J = 80 and K a = 33 through a frequency of 633 GHz. The newly measured transitions were added to approximately 200 previously reported and now unambiguously assigned microwave transitions to comprise a data set of 2390 transitions which has been fit to 59 kHz using a reduced axis method (RAM) Hamiltonian. The ground state has been confirmed to consist of a symmetric and an antisymmetric gauche conformer with no spectroscopic evidence of stable trans conformer. A complete set of rotation and distortion constants through 6th order and a number of the 8th and one 10th order constants for the normal species are presented along with those determined from a re-analysis of the existing OD species data. The a and b symmetry Coriolis interaction constants and the gauche + gauche − tunnelling frequency of 652389.4 MHz has been determined for the OH species while the b symmetry Coriolis interaction and the 213 480 MHz tunnelling frequency were determined for the OD species.

Power series expansions of water eigenstate energies in J and K converge poorly and show alternating signs of the coefficients of the power series. Euler series can be used effectively to change an alternating series into one where all the coefficients have the same sign and where the radius of convergence is increased. This paper extends the Euler series to a two-dimensional series in K 2 and [ J ( J + 1) − K 2 ]. Application of this Euler series to the rotational energies of the ground state and the first 4 excited vibrational states of water allows a fit to experimental accuracy to J = 22 and K = 22. This fit has good convergence and also has predictive capability. It is much easier to fit the perturbed states because the Euler series allows the zero-order energy the perturbed states to be predicted with more confidence.

We report an investigation of the rotational-torsional spectrum of the gauche rotational isomers of ethyl alcohol in the 51-505 GHz frequency region. Over a thousand transitions between rotational levels in the gauche substates of the ground OH torsional state have been measured and assigned. These transitions involve rotational quantum numbers J and K(sub a) up to 30 and 15, respectively, and are of two types: alpha-type transitions between levels in either the gauche+ or the gauche-substate, and c-type transitions between rotational levels in the different substates. The majority of these transitions have been fit satisfactorily using a two-state Hamiltonian based on the Fixed Framework Axis Method (FFAM). The rotation, distortion, and interaction constants have been determined along with the energy difference between the two gauche substates. The derived constants can be used to predict many more transitions accurately for astronomical purposes. The J and K(sub a) region where the two-state analysis can be used has been determined. The basis for a three-state analysis including the trans substate is presented and the applicability of the FFAM approach is discussed.

$^{1}$E. Hirota, {J. Chem. Phys}. 45, 1984-1990 (1957). $^{2}$ D.R. Lide, JR. and D. E. Mann, {J. Chem. Phys}. 27, 868-873 (1957).