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The synergy between high-resolution rotational spectroscopy and quantum-chemical calculations is essential for exploring future detection of molecules, especially when spectroscopy parameters are not available yet. By using highly correlated ab initio quartic force fields (QFFs) from explicitly correlated coupled cluster theory, a complete set of rotational constants and centrifugal distortion constants for $ {D2CS} $ D 2 CS and cis/trans-DCSD isomers have been produced. Comparing our new ab initio results for $ {D_2CS} $ D 2 CS with new rotational spectroscopy laboratory data for the same species, the accuracy of the computed B and C rotational constants is within 0.1% while the A constant is only slightly higher. Additionally, quantum chemical vibrational frequencies are also provided, and these spectral reference data and new experimental rotational lines will provide additional references for potential observation of these deuterated sulfur species with either ground-based radio telescopes or space-based infrared observatories. [ABSTRACT FROM AUTHOR]

The enhancement of a cryogenic radio frequency 22 pole trap instrument by the addition of ring electrodes is presented in detail. The ring electrodes tightly surround the poles and only a fraction of the applied electric potential penetrates to the trap axis, facilitating the fine control of slow cold ions. A precise computational model, describing the effective mechanical potential created by the applied static and rf fields, governing the ion behaviour, is employed to demonstrate and understand the operation of our setup. The use of ring electrodes for improved extraction of cold stored ions is shown. Variable trapping potentials, placed on one ring electrode, can be used to control the evaporation of only those $ \mbox {H}^{+} $ H + ions from the trap, whose kinetic energy exceeds the barrier. This ring electrode trapping opens new possibilities to study processes of minimal kinetic energy release, e. g. spin exchange. We propose a robust modified method for the determination of temperature dependent ion molecule reaction rates, resistant to effects caused by neutral gas freezing and demonstrate it on the reaction of $ \mbox {CO}^{+}/{\mbox {CO}_{2}}^{+} $ CO + / CO 2 + with $ \mbox {H}_{2}/ $ H 2 / $ \mbox {D}_{2} $ D 2 . Finally, the use of a supercontinuum laser for quick localisation of spectroscopic bands is examined on the $ {\mbox {N}_{2}}^{+} $ N 2 + Meinel system. [ABSTRACT FROM AUTHOR]

We report the gas-phase detection and spectroscopic characterisation of ethynethiol (), a metastable isomer of thioketene () using a combination of Fourier-transform microwave and submillimetre-wave spectroscopies. Several a-type transitions of the normal species were initially detected below 40 GHz using a supersonic expansion-electrical discharge source, and subsequent measurement of higher-frequency, b-type lines using double resonance provided accurate predictions in the submillimetre region. With these, searches using a millimetre-wave absorption spectrometer equipped with a radio frequency discharge source were conducted in the range 280–660 GHz, ultimately yielding nearly 100 transitions up to and. From the combined data set, all three rotational constants and centrifugal distortion terms up to the sextic order were determined to high accuracy, providing a reliable set of frequency predictions to the lower end of the THz band. Isotopic substitution has enabled both a determination of the molecular structure of HCCSH and, by inference, its formation pathway in our nozzle discharge source via the bimolecular radical-radical recombination reaction , which is calculated to be highly exothermic (−477 kJ/mol) using the HEAT345(Q) thermochemical scheme. [ABSTRACT FROM AUTHOR]